CN107275475B - A kind of TiO2@PZT nano-wire array/polymer composite dielectric material and preparation method thereof - Google Patents
A kind of TiO2@PZT nano-wire array/polymer composite dielectric material and preparation method thereof Download PDFInfo
- Publication number
- CN107275475B CN107275475B CN201710564172.5A CN201710564172A CN107275475B CN 107275475 B CN107275475 B CN 107275475B CN 201710564172 A CN201710564172 A CN 201710564172A CN 107275475 B CN107275475 B CN 107275475B
- Authority
- CN
- China
- Prior art keywords
- nano
- tio
- pzt
- wire array
- polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000002070 nanowire Substances 0.000 title claims abstract description 95
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 239000002131 composite material Substances 0.000 title claims abstract description 57
- 229920000642 polymer Polymers 0.000 title claims abstract description 50
- 239000003989 dielectric material Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000010410 layer Substances 0.000 claims abstract description 50
- 239000000463 material Substances 0.000 claims abstract description 41
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000000758 substrate Substances 0.000 claims abstract description 19
- 238000000137 annealing Methods 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 10
- 239000013047 polymeric layer Substances 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 44
- 239000010936 titanium Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 13
- 239000002243 precursor Substances 0.000 claims description 13
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 12
- 238000010792 warming Methods 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical class [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 3
- 150000007522 mineralic acids Chemical class 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 241000790917 Dioxys <bee> Species 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 150000004767 nitrides Chemical class 0.000 claims 1
- 229910052719 titanium Inorganic materials 0.000 claims 1
- 239000000919 ceramic Substances 0.000 abstract description 17
- 238000004146 energy storage Methods 0.000 abstract description 7
- 239000011159 matrix material Substances 0.000 abstract description 5
- 238000002156 mixing Methods 0.000 abstract description 2
- 239000002033 PVDF binder Substances 0.000 description 13
- 230000005684 electric field Effects 0.000 description 13
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 13
- 238000004528 spin coating Methods 0.000 description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 230000010287 polarization Effects 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- 239000004408 titanium dioxide Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229940046892 lead acetate Drugs 0.000 description 4
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 4
- 239000003990 capacitor Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 229920001897 terpolymer Polymers 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- PMTRSEDNJGMXLN-UHFFFAOYSA-N titanium zirconium Chemical compound [Ti].[Zr] PMTRSEDNJGMXLN-UHFFFAOYSA-N 0.000 description 2
- 229920001780 ECTFE Polymers 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- 229910002370 SrTiO3 Inorganic materials 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- PNZVFASWDSMJER-UHFFFAOYSA-N acetic acid;lead Chemical compound [Pb].CC(O)=O PNZVFASWDSMJER-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000002457 bidirectional effect Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 230000019771 cognition Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002305 electric material Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000005621 ferroelectricity Effects 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical compound FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- PQIOSYKVBBWRRI-UHFFFAOYSA-N methylphosphonyl difluoride Chemical group CP(F)(F)=O PQIOSYKVBBWRRI-UHFFFAOYSA-N 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 235000012149 noodles Nutrition 0.000 description 1
- 238000005325 percolation Methods 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920000131 polyvinylidene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/80—Constructional details
- H10N30/85—Piezoelectric or electrostrictive active materials
- H10N30/852—Composite materials, e.g. having 1-3 or 2-2 type connectivity
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/80—Constructional details
- H10N30/85—Piezoelectric or electrostrictive active materials
- H10N30/857—Macromolecular compositions
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N35/00—Magnetostrictive devices
- H10N35/01—Manufacture or treatment
Landscapes
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Insulating Materials (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a kind of TiO2@PZT nano-wire array/polymer composite dielectric material, including TiO2Nano-wire array, PZT clad and polymeric layer.In addition, first growing TiO in substrate surface the invention also discloses the preparation method of the composite material2Nano-wire array layer；PZT colloidal sol is coated on its surface again, is then made annealing treatment, finally the TiO after compound again2Nano-wire array layer surface coated polymer solution is drying to obtain the composite dielectric material.Material use provided by the invention has the TiO of height-oriented property2Nano-wire array is as substrate, PZT phase is coated on the surface of nano wire, again in upper layer spin on polymers again, existing composite dielectric material can be overcome generally existing because dielectric properties difference caused by ceramic phase and polymer matrix compatability are bad, mixing is uneven etc. technical problem；By the collaboration of each layer structure, the dielectric properties that can efficiently promote composite material and the energy storage density under existing fringing field.
Description
Technical field
The present invention relates to a kind of nano combined dielectric materials of three-phase, specifically with TiO2@PZT nano-wire array is filler,
With the compound obtained dielectric composite material of polymer.
Background technique
High-performance dielectric composite material is widely used in the modern microelectronics such as capacitor, memory, transistor, communication device
Devices field.In order to realize the miniaturization and adaptability of dielectric composite material, it is desirable that it has high relative dielectric constant, low simultaneously
Dielectric loss, high energy storage density and excellent processability.In recent years, polymer matrix ceramic dielectric composite material is due to comprehensive ceramics
With the advantages such as the high dielectric constant of polymer and low-dielectric loss and one of become research hotspot.The ceramics of addition, which generally have, to be received
Meter ruler cun, high surface energy makes it be difficult to be uniformly dispersed in high-viscosity polymer and insecure in conjunction with matrix, to can draw
Enter many defects, causes the anti-breakdown electric field of dielectric composite to reduce, greatly limit the raising of its energy storage density.It solves this
A kind of method of problem is exactly that ceramic grain surface is surface modified or is coated, and improves its in a polymer matrix compatible
Property and dispersibility, reduce both interface there is a possibility that defect.
For example, the Chinese patent document of Publication No. CN1587206A discloses a kind of piezoelectric ceramics and Polymeric dielectric is multiple
The preparation method of condensation material, this method required piezoelectric ceramic piece crush or quenching after be sieved, by obtained ceramic powders and
Thermoplastic polymer is uniformly mixed, and piezoelectric ceramics and Polymeric dielectric composite material is made in compression moulding, microwave irradiation after drying.
In addition, the Chinese patent document of Publication No. CN104496491A discloses a kind of dielectric composite material, including pressure
Electroceramics and polyvinylidene fluoride (PVDF), mass percentage composition are as follows: piezoelectric ceramics 50%~98% gathers inclined difluoro second
Alkene 2%~50%；It is also added with pressure sensitive, the pressure sensitive accounts for piezoelectric ceramics and polyvinylidene fluoride total weight
0.1%~10%.The voltage-sensitive ceramic is ZnO, SnO2、TiO2、 SrTiO3Etc. one of systems or several.On but
Stating both of which there is a problem of corresponding, and the volume fraction of one ceramic particle in the polymer is limited, when being added
Ceramic particle reach percolation threshold nearby will will appear conducting phenomenon, sample can be made breakdown, the property such as performance of ferroelectric piezoelectric
It can be unsatisfactory.
Currently, widely being paid close attention to for the research of one-dimensional ceramic nano line, nanometer rods by everybody, and also achieve phase
The progress answered, but dielectric constant acquired by existing compound and polarization are all relatively low, due to dielectric constant and polarize all
Dielectric properties and energy-storage property are influenced, so further increasing the dielectric constant of compound and polarization is necessary.
Summary of the invention
The technical issues of to overcome the prior art to encounter, the present invention provides a kind of TiO2@PZT nano-wire array/polymerization
The composite dielectric material of object, it is intended to promote the dielectric constant of material, polarization intensity, the performances such as energy density.
In addition, the present invention also provides a kind of TiO2The preparation of@PZT nano-wire array/polymer composite dielectric material
Method, it is intended to stablize the composite dielectric material for preparing the high energy-storage property.
The present inventor is had found by numerous studies, substitutes existing common cognition as substrate filler using nano-wire array
Ceramic particle, can unexpectedly promote the performance of composite material, then coordinated in other materials, can further be promoted multiple
Close the dielectric properties of obtained material: the technology of the present invention technical solution is as follows:
A kind of TiO2@PZT nano-wire array/polymer composite dielectric material, including successively compound TiO2Nanometer linear array
Column, PZT layers and polymeric layer.
The dielectric material of three-phase composite of the present invention has high dielectric constant, high polarization intensity, and in existing fringing field
Under obtain high-energy density.A kind of new approaches are opened for the design of capacitor of new generation, are had great importance.
Composite dielectric material of the present invention is initially formed the TiO2Nano-wire array, TiO2Nano-wire array surface
PZT layers are compounded to form, is then compounded to form polymeric layer at PZT layers again.Composite dielectric material structure novel of the present invention；
Originally by the way of ceramic material array, overcome the existing dispersion performance generally existing using granular materials bad, holds
Easily there is conducting phenomenon, composite material is easy breakdown, the performance technologies problem such as performance of ferroelectric piezoelectric.
The energy storage material with Three phase nano-complex provided by the invention, using having height-oriented property
TiO2Nano-wire array is as substrate, then PZT phase is coated on the surface of nano wire, again in upper layer spin on polymers, can gram
Take existing composite dielectric material it is generally existing because ceramic phase and polymer matrix compatability are bad, mixing is uneven etc. caused by
The technical problem of dielectric properties difference；By the collaboration of each layer structure, the dielectric properties of composite material, example can be efficiently promoted
Dielectric constant, polarization intensity and the energy density of composite material is such as substantially improved, and keeps relatively high effective transfer efficiency.
Preferably, the TiO2Nano-wire array is by several TiO along the growth of substrate vertical direction2Nano wire composition.
In the present invention, the nano-wire array is also perpendicular to the plane of base material, the TiO of such high orientation2It receives
The direction of rice noodles is parallel with direction of an electric field, can further promote the dielectric constant and anti-breakdown electric field of the composite material.
TiO of the present invention2In nano-wire array, the TiO2Extend basis space in nanowire length direction；?
It is TiO2The length direction of nano wire and the angle of substrate are preferably greater than 0 degree, less than 180 degree；Further preferably 60~
120 degree.Most preferably, the TiO2Nano wire is vertical or is approximately perpendicular to base plane.
Preferably, TiO2In nano-wire array, TiO2Nanowire length is 2~4 μm, and diameter is 50~70nm.
The PZT layer can be coated in TiO by PZT colloidal sol2Nano-wire array surface, subsequent annealed processing, forms institute
The PZT layer stated.
PZT layers with a thickness of 5-20nm.
Preferably, the material of the polymeric layer is P (VDF-TrFE-CTFE) Kynoar terpolymer
(also referred to as are as follows: poly- (vinylidene fluoride-trifluoro-ethylene-chloro trifluoro ethylene)), P (VDF-HFP) (Kynoar hexafluoropropene),
At least one of PVDF (Kynoar).
Further preferably, the material of the polymeric layer is P (VDF-TrFE-CTFE) Kynoar ternary polymerization
Object.Performance using the polymeric layer of the preferred polymer is more excellent, for example, dielectric constant and polarization intensity it is bigger.
Preferably, polymer layer of thickness is 4~6 μm.
Preferably, TiO of the present invention2Nano-wire array/PZT/ polymer composite dielectric material, entire compound Jie
Electric material with a thickness of 6~10 μm；Preferably 6~8 μm.
In addition, the present invention also provides the TiO described in one kind2@PZT nano-wire array/polymer composite dielectric material
Preparation method, first substrate surface growth, formed TiO2Nano-wire array layer；Again in TiO2The coating of nano-wire array layer surface
PZT colloidal sol is then made annealing treatment, thus in TiO2Nano-wire array layer surface forms PZT layers；Finally again in PZT layers of table
Face coated polymer solution is drying to obtain the composite dielectric material.
In the present invention, TiO is successively compounded to form in substrate material surface2Nano-wire array layer, PZT layers and polymeric layer,
Base material is then removed again, and the composite dielectric material is made.
Preferably, TiO2The preparation process of nano-wire array layer are as follows:
Titanate esters and acid solution are mixed into obtain precursor solution；In precursor solution, control Ti concentration be 0.5~
1.0moL/L；Base material is put into precursor solution, and the hydro-thermal reaction at 160~200 DEG C；After hydro-thermal reaction, take out
Growth has the base material of titanium dioxide nanowire array layer, dry, thus in substrate material surface composite Ti O2Nanometer linear array
Column layer.
The existing common raw material that can be hydrolyzed in acid solution can be used in the titanate esters.
Preferably, titanate esters are at least one of butyl titanate, tetraethyl titanate, tetraisopropyl titanate.
Further preferably, the titanate esters are butyl titanate.
The acid solution is the aqueous solution of water-soluble organic acid, inorganic acid.
For example, the water-soluble organic acid is, for example, at least one of HAc, nitric acid, sulfuric acid.
The water-soluble inorganic acid is, for example, hydrochloric acid.
Preferably, the acid solution is hydrochloric acid.
Preferably, Pb: Zr: Ti molar ratio is 1.0~1.2: 0.50~0.55: 0.45 in the PZT colloidal sol
~0.55.
Further preferably, in the PZT colloidal sol, the molar concentration of PZT is 0.1~0.2mol/L.
Preferably, annealing process are as follows: be first warming up to 180~220 DEG C with the rate of 8~12 DEG C/min, and keep the temperature 5
~10min is then warming up to 330~380 DEG C with the rate of 4~8 DEG C/min, and after keeping the temperature 5~10min again with 8~12 DEG C/
The rate of min is warming up to 390~420 DEG C, and keeps the temperature 5~10min；Finally 550 are warming up to the rate of 8~12 DEG C/min again
~650 DEG C, and keep the temperature 5~12min.
Existing conventional means, such as spin coating can be used in coating method of the present invention.
Preparation method of the present invention, specifically includes the following steps:
Step (1): titanate esters and acid solution mix to obtain precursor solution, and in precursor solution, the concentration of Ti is 0.5~
1.0moL/L；Base material is put into precursor solution, and the hydro-thermal reaction at 160~200 DEG C；After hydro-thermal reaction, take out
Growth has the base material of titanium dioxide nanowire array layer, dry, thus in substrate material surface composite Ti O2Nanometer linear array
Column layer；
Step (2): PZT colloidal sol is coated in the titanium dioxide nanowire array layer surface of step (1), followed by annealing
Processing, thus in TiO2Nano-wire array layer surface coats one layer of PZT；
Step (3): in the pzt thin film layer surface coated polymer solution of step (2), it is drying to obtain the composite dielectric
Material.
In the present invention, under the presoma Ti concentration, cooperate the hydro-thermal reaction at the temperature, it can be in base material table
Look unfamiliar the long TiO for being approximately perpendicular to base plane2Nano wire；Then again coordinated in step (2) PZT colloidal sol Pb: Zr
: the molar ratio and annealing program of Ti can help to the composite material that high dielectric property is prepared.
The present inventor is practiced by many experiments and is found, the concentration of the Ti in presoma will affect the shape of nano-wire array
Looks also will affect the consistency of nano-wire array；And then influence the dielectric properties of composite material obtained.
Preferably, the concentration of Ti is 0.5~0.7moL/L.
Preferably, the base material is FTO glass.
The precursor solution is subjected to hydro-thermal reaction, only needs to take out base material after reaction, and be dried
Processing can be compounded to form TiO in substrate material surface2Nano-wire array；Without excessive operation bidirectional, preparation process is simple.
Preferably, the temperature of hydro-thermal reaction is 170~190 DEG C.
Preferably, the hydro-thermal reaction time is 2~4h under the presoma and hydrothermal temperature；Further
Preferably 3h.
Further preferably, in step (1), one kind preferably growing TiO in base material2Nano wire, preparation TiO2It receives
The step of nanowire arrays: the concentrated hydrochloric acid that mass fraction is 36%~38% is mixed with isometric deionized water, obtains acid solution；To
Butyl titanate to be added in the acid solution, stirs to obtain precursor solution, the concentration for controlling Ti in precursor solution is 0.5~
1.0mol/L；Then heating is in 170~190 DEG C of 2~4h of progress hydro-thermal reaction；After hydro-thermal reaction, base material is taken out, and carry out
It is dried to obtain the final product.
In the present invention, prepare PZT colloidal sol method it is preferred are as follows: according to Pb: Zr: Ti molar ratio weigh lead acetate, zirconium nitrate,
Butyl titanate；Certain acetylacetone,2,4-pentanedione is added dropwise in beaker and makees stabilizer and ethylene glycol monomethyl ether solvent, then adds required weight
Butyl titanate and zirconium nitrate, abundant heating stirring to clarify zirconium titanium salt mixed solution；Lead acetate is then added dropwise again
Acetum persistently stirs 2~3h, 1~2h of ultrasound obtains the PZT colloidal sol.
In the present invention, under the PZT colloidal sol, cooperate the annealing process, can help to be made it is compound good and
Have both the pzt thin film layer of superior ferroelectric and piezoelectricity.
In step (2), the PZT colloidal sol is preferably passed through into spin coating instrument and is spin-coated on TiO2The surface of nano-wire array layer,
Preferably, the revolving speed of spin coating process is 250~350r/min, the single spin time is 10~20s, and spin coating number is 4~6
It is secondary.
It is made annealing treatment after spin coating, preferably, annealing process are as follows: 200 DEG C first are warming up to the rate of 10 DEG C/min,
And keep the temperature 5min；350 DEG C then are warming up to the rate of 6 DEG C/min, and keeps the temperature 5min；It is heated up after again with the rate of 10 DEG C/min
To 400 DEG C, and keep the temperature 5min；600 DEG C finally are warming up to the rate of 10 DEG C/min again, and keeps the temperature 8min.
After annealing, then in pzt thin film layer surface coated polymer solution obtained.
Preferably, the polymer solution is P (VDF-TrFE-CTFE), P (VDF-HFP), in PVDF at least
A kind of DMF- acetone mixture.
The polymer solution is at least one of P (VDF-TrFE-CTFE), P (VDF-HFP), PVDF polymer
It is dissolved in solution obtained by the mixed solvent of DMF and acetone.
Preferably, the polymer solution is the solution of the DMF- acetone of P (VDF-TrFE-CTFE).
Preferably, the concentration of polymer is 7~9wt% in polymer solution.
In the present invention, the polymer solution is preferably spin-coated on to the surface of pzt thin film layer by spin coating instrument, as excellent
Choosing, the revolving speed of spin coating process are 250~350r/min, and the single spin time is 10~20s, and spin coating number is 2~4 times.
After the completion of polymer solution spin coating, in 60~80 DEG C of at a temperature of dry, the obtained composite dielectric material.
The present invention uses non-ferroelectric TiO2On the one hand nano-wire array can reduce dielectric mismatch degree, mention as substrate
On the other hand high-compatibility is conducive to synthesize, and have height-oriented, helps to improve the dielectric properties of material.
The present invention is using the PZT and the TiO for having high dielectric constant, high polarization intensity2Nano-wire array collaboration is matched
It closes, the nano-wire array of the titanium dioxide nano thread surface cladding PZT with excellent properties can be obtained.Compared to existing technology
Scheme, preparation method of the present invention is simple, and material obtained is had excellent performance.
The three-phase of PZT and P (VDF-TrFE-CTFE) described in height-oriented titanium dioxide nanowire array, cooperation
Composite construction can cooperate with there are multiple interfaces and promote interfacial polarization, to improve dielectric properties.
Beneficial effects of the present invention
A kind of novel dielectric composite construction is proposed in the present invention, using TiO2Nano-wire array can be improved for substrate
The dielectric constant of compound and anti-breakdown electric field, and preparation process is simple, and can mention because its dielectric constant is lower
The high compatibility with polymer.Sandwich structure proposed by the present invention provides the structure design about dielectric capacitor of new generation
New view.
The present invention utilizes the TiO for having height-oriented property2Nano-wire array coats one layer as substrate, in nanowire surface
PZT, the three-phase nano composite structure that upper layer is P (VDF-TrFE-CTFE) polymer film, entire complex thin film uniform color are flat
It is whole smooth.
The present invention is by TiO2Nano-wire array is as substrate, hence it is evident that improves dispersibility and compatibility in the polymer.
The dielectric constant for the dielectric composite that the present invention obtains significantly increases, and has low dielectric loss.
The dielectric composite that the present invention obtains have excellent dielectric properties, prepared dielectric composite material at room temperature,
When test frequency is 1KHz, dielectric constant is up to 220.
Defect is few in the dielectric composite material that the present invention obtains, and has excellent mechanical performance.
In the present invention, the energy density of nano combined dielectric material obtained is 3.99~6.87J/cm3, effectively convert effect
Rate reaches 58.1~59.7%, and it is 14.22 μ~23.35C/cm that maximum potential, which is moved,2；Material of the present invention has Gao Jie
The advantages such as electric constant, high polarization intensity, high energy storage density.
Detailed description of the invention
Fig. 1 is TiO prepared by embodiment 12@PZT nano-wire array/P (VDF-TrFE-CTFE) three-phase nano-complex
TiO2The surface SEM of@PZT nano-wire array schemes；
Fig. 2 is TiO prepared by embodiment 12@PZT nano-wire array/P (VDF-TrFE-CTFE) three-phase nano-complex
TiO2The section SEM of@PZT nano-wire array schemes；
Fig. 3 is that TiO2@PZT nano-wire array/P (VDF-TrFE-CTFE) three-phase nano-complex made from embodiment 1 is disconnected
Face microscopic appearance figure；
Fig. 4 is that TiO2@PZT nano-wire array/P (VDF-TrFE-CTFE) three-phase made from Examples 1 to 3 is nano combined
Object dielectric constant detection data figure；
Fig. 5 is that TiO2@PZT nano-wire array/P (VDF-TrFE-CTFE) three-phase made from Examples 1 to 3 is nano combined
Ferroelectric hysteresis loop of the object under not same electric field.
Fig. 6 is TiO made from embodiment l~32@PZT nano-wire array/P (VDF-TrFE-CTFE) three-phase is nano combined
Energy density and efficiency chart of the object under not same electric field.
Fig. 7 is the dielectric constant data fitted figure of material made from comparative example 1~4；
Fig. 8 is the dielectric loss data fitted figure of material made from comparative example 1~4；
Fig. 9 is the energy density data fitted figure of material made from comparative example 1~4；
Figure 10 is the section SEM figure of material made from comparative example 1.
As can be seen from Figure 1: TiO2@PZT nano-wire array still maintains the pattern basically perpendicular to FTO substrate, and
It is quite neat.As can be seen from Figure 2: in TiO2@PZT nano-wire array/P (VDF-TrFE-CTFE) three-phase nano-complex
In, TiO2The defects of arrangement of@PZT nano-wire array layer is close, does not see apparent crackle, hole.
As can be seen from Figure 4: when the source Ti concentration be 0.5mol/L when, prepared dielectric composite material at room temperature, test
When frequency is 1KHz, dielectric constant 168.7, when the concentration in the source Ti is 0.7mol/L is situated between under same frequency condition
Electric constant increases to 198.3, and when the concentration in the source Ti is 1.0mol/L, dielectric constant reaches maximum value 218.9..
From Fig. 5~6 it can be seen that
Under the current field condition of 100kV/mm, the source Ti concentration is that the nano-complex of 0.5mol/L obtains 3.99J/cm3
Energy density, effective transfer efficiency reaches 58.1%, and it is 14.22 μ C/cm that maximum potential, which is moved,2, when the source Ti, concentration increases to
When 0.7mol/L, under the current field condition of 130kV/mm, 5.99J/cm is obtained3Energy density, effective transfer efficiency reaches
To 59.7%, it is 18.38 μ C/cm that maximum potential, which is moved,2.When the concentration in the source Ti is 1.0mol/L, in the electric field item of 143kV/mm
Maximum energy density values 6.87J/cm is obtained under part3, it is 23.35 μ C/cm that maximum potential, which is moved,2。
Specific embodiment
In the embodiment of the present invention, prepared dielectric composite wood is tested using Agilent 4294A LCR impedance analyzer
The dielectric constant and dielectric loss of material at room temperature, test frequency increase to 10MHz from 1kHz.Utilize TF Analyzer
2000FE ferroelectricity analyzer tests the ferroelectric hysteresis loop of dielectric composite under not same electric field, and it is close to calculate corresponding energy
Degree.
Embodiment 1
TiO2The preparation of@PZT nano-wire array/P (VDF-TrFE-CTFE) three-phase nano-complex
Step (1): preparation concentrated hydrochloric acid 25ml, deionized water 25ml first is mixed 3~5 minutes, then adds metatitanic acid
Four butyl esters, stirring 5 minutes mixed solution, control mixed solution in butyl titanate concentration be 0.5mol/L, then after will mix
It closes solution to pour into reaction kettle, and preprepared FTO electro-conductive glass is placed in reaction kettle, react 3h at 180 DEG C.
FTO electro-conductive glass after taking out reaction is put into drying 5 minutes in drying box, at this time long good TiO above FTO electro-conductive glass2
Nano-wire array.TiO2Nanowire length is 2~4 μm, and diameter is 50~70nm.
Step (2): then prepare PZT colloidal sol, weigh suitable lead acetate, zirconium nitrate, butyl titanate so that three kinds from
Molar ratio Pb: Zr: Ti 1.1: 0.52: 0.48 of son, since butyl titanate is unstable, so being added dropwise 3 in beaker first
~4 drop acetylacetone,2,4-pentanediones make stabilizer, and weighed butyl titanate and zirconium nitrate are dissolved in suitable ethylene glycol monomethyl ether, sufficiently added
Thermal agitation to solution is clarified, and lead acetate is dissolved in glacial acetic acid, and 120 DEG C of baking 5min remove the crystallization water after heating stirring, by acetic acid
Lead solution is added drop-wise to dropwise in the mixed solution of zirconium titanium salt, stirs to form light yellow clear precursor solution when being added dropwise, stirring 2
~3h uses preceding ultrasonic disperse 1h；Obtain PZT colloidal sol (PZT concentration is 0.2mol/L).The FTO leaching of nano-wire array will have been grown
Stain 3min in the PZT colloidal sol prepared, then carries out spin coating, revolving speed 300r/min, time 15s again, and spin coating number is 2 times.
Drying 10 minutes in 80 DEG C of drying boxes are put it into after the completion of spin coating, at wet film.Then by sample be put into tubular annealing furnace into
Row annealing, annealing are divided into four-stage, and first stage first keeps the temperature 5 minutes at 200 DEG C, and then second stage heats up
To 350 DEG C, 5 minutes are kept the temperature, three phases are warming up to 400 DEG C again, keep the temperature 5 minutes, and the last stage is raised to 600 DEG C, protect
Temperature 8 minutes.Wherein one, three, four stage heating rates are 10 DEG C/min, and second stage is 6 DEG C/min.It is obtained after annealing
TiO2The surface SEM figure of@PZT nano-wire array is shown in Fig. 1；Section SEM figure is shown in Fig. 2；
Step (3): preparing Kynoar terpolymer solution, (P (VDF-TrFE-CTFE) Kynoar ternary is total
Polymers), i.e., Kynoar terpolymer is dissolved in mixed solution obtained in acetone and dimethylformamide (DMF),
The volume ratio of middle acetone and dimethylformamide is 7: 3, and the mass fraction of Kynoar is 8% in Kynoar solution.
The Kynoar solution prepared is spin-coated on sample, revolving speed 300r/min, time 15s, spin coating 2 times.Then by sample
Product are put into drying box at 70 DEG C dry 10h.TiO obtained2@PZT nano-wire array/P (VDF-TrFE-CTFE) three-phase nanometer
Compound is labeled as TiO2@PZT NA1；The SEM figure of its section compound is shown in Fig. 3.Titanium dioxide nano thread passes through PZT colloidal sol
Nano-wire array after cladding with a thickness of 3 microns, entire polymer with a thickness of 7 microns.
Designing round bore dia is 2mm, and Kong Yuanxin spacing is the metal mask plate of 3mm, the metal mask plate shape side of being positive
Shape, side length 30mm.The complexes membrane suppressed is clipped among 2 metal mask plates, upper and lower surface symmetrically sputters gold electrode,
Upper and lower surface sputtering time is 10min, guarantees that gold electrode has enough thickness, sputtering electrode tests electrical property respectively.
The dielectric constant detection data of material obtained is as shown in Figure 4.The not ferroelectric hysteresis loop under same electric field and different electricity
Energy density and efficiency chart off field is shown in Figures 5 and 6 respectively.
Embodiment 2
It is compared with embodiment 1, difference is, in step (1), controls the concentration of butyl titanate in solution of tetrabutyl titanate
For 0.7mol/L.TiO obtained2@PZT nano-wire array/P (VDF-TrFE-CTFE) three-phase nano-complex is labeled as TiO2@
PZT NA2.Nano-wire array of the titanium dioxide nano thread after PZT Sol-gel Coated is with a thickness of 3 microns, entire polymer
With a thickness of 7 microns.The dielectric constant detection data of material obtained is as shown in Figure 4.The not ferroelectric hysteresis loop under same electric field
And the energy density under same electric field and efficiency chart are not shown in Figures 5 and 6 respectively.
Embodiment 3
It is compared with embodiment 1, difference is, in step (1), controls the concentration of butyl titanate in solution of tetrabutyl titanate
For 1.0mol/L.
TiO2@PZT nano-wire array/P (VDF-TrFE-CTFE) three-phase nano-complex is labeled as TiO2@PZT NA3。
Nano-wire array of the titanium dioxide nano thread after PZT Sol-gel Coated is with a thickness of 3 microns, the thickness of entire polymer
For 7 microns.The dielectric constant detection data of material obtained is as shown in Figure 4.The not ferroelectric hysteresis loop under same electric field and not
Energy density and efficiency chart under same electric field are shown in Figures 5 and 6 respectively.
Comparative example 1
It is compared with embodiment 1, difference is, that polymer is chosen is PVDF, and the concentration of PZT colloidal sol is 0.5M,
TiO2The Ti concentration of nano-wire array is 0.5mol/L, TiO obtained2Nano-wire array/PZT/PVDF composite material, is labeled as
PZT@0.5TO.Section made from this comparative example is shown in Figure 10, titanium dioxide nano thread with a thickness of 3 microns, PZT colloidal sol it is dense
Degree is big, in TiO2The PZT layer of nano-wire array surface recombination with a thickness of 5 microns, entire polymer with a thickness of 12 microns
Left and right.Its dielectric constant (Fig. 7), dielectric loss (Fig. 8) and energy density (Fig. 9), from relevant experimental data, this comparison
The performance of material made from example is significantly worse than three-phase nano-complex prepared by the present invention.
Comparative example 2
It is compared with embodiment 1, difference is, that polymer is chosen is PVDF, and the concentration of PZT colloidal sol is 0.5M,
TiO2The Ti concentration of nano-wire array is 0.7mol/L, TiO obtained2Nano-wire array/PZT/PVDF composite material, is labeled as
PZT@0.7TO.Its dielectric constant (Fig. 7), dielectric loss (Fig. 8) and energy density (Fig. 9), from relevant experimental data, this
The performance of material made from comparative example is significantly worse than three-phase nano-complex prepared by the present invention.
Comparative example 3
It is compared with embodiment 1, difference is, that polymer is chosen is PVDF, and the concentration of PZT colloidal sol is 0.5M,
TiO2The Ti concentration of nano-wire array is 1.0mol/L, TiO obtained2Nano-wire array/PZT/PVDF composite material, is labeled as
PZT@1.0TO.Its dielectric constant (Fig. 7), dielectric loss (Fig. 8) and energy density (Fig. 9), from relevant experimental data, this
The performance of material made from comparative example is significantly worse than three-phase nano-complex prepared by the present invention.
Comparative example 4
It is compared with embodiment 1, difference is, not in TiO2Composite PZT layer between nano-wire array and PVDF layers；This
The material marking of comparative example is 0.5TO.
Claims (5)
1. a kind of TiO2@PZT nano-wire array/polymer composite dielectric material, which is characterized in that including successively compound
TiO2Nano-wire array, PZT layers and polymeric layer；
The TiO2Nano-wire array is by several TiO along the growth of substrate vertical direction2Nano wire composition；
TiO2In nano-wire array, TiO2Nanowire length is 2~4 μm, and diameter is 50~70nm；
PZT layers with a thickness of 5-20nm；
The material of the polymeric layer is P (VDF-TrFE-CTFE).
2. TiO as described in claim 12@PZT nano-wire array/polymer composite dielectric material, which is characterized in that polymerization
Nitride layer is with a thickness of 4~6 μm.
3. a kind of TiO of any of claims 1 or 22The preparation method of@PZT nano-wire array/polymer composite dielectric material,
It is characterized in that, first in substrate surface growth, formation TiO2Nano-wire array layer；Again in TiO2The coating of nano-wire array layer surface
PZT colloidal sol is then made annealing treatment, thus in TiO2Nano-wire array layer surface forms PZT layers；Finally again in PZT layers of table
Face coated polymer solution is drying to obtain the composite dielectric material；
TiO2The preparation process of nano-wire array layer are as follows:
Titanate esters and acid solution are mixed into obtain precursor solution；In precursor solution, the concentration for controlling Ti is 0.5~1.0moL/L；
Base material is put into precursor solution, and the hydro-thermal reaction at 160~200 DEG C；After hydro-thermal reaction, taking out growth has dioxy
Change the base material of titanium nano-wire array layer, it is dry, thus in substrate material surface composite Ti O2Nano-wire array layer；
In the PZT colloidal sol, the molar ratio of Pb:Zr:Ti is 1.0~1.2:0.50~0.55:0.45~0.55；
The molar concentration of PZT colloidal sol is 0.1~0.2mol/L；
Annealing process are as follows: be first warming up to 180~220 DEG C with the rate of 8~12 DEG C/min, and keep the temperature 5~10min；Then
330~380 DEG C are warming up to the rate of 4~8 DEG C/min, and keeps the temperature 5~10min；It is heated up after again with the rate of 8~12 DEG C/min
To 390~420 DEG C, and keep the temperature 5~10min；550~650 DEG C finally are warming up to the rate of 8~12 DEG C/min again, and keeps the temperature 5
~12min；
The polymer solution is the DMF- acetone mixture of P (VDF-TrFE-CTFE).
4. the TiO as claimed in claim 32The preparation side of@PZT nano-wire array/polymer composite dielectric material
Method, it is characterised in that；Titanate esters are at least one of butyl titanate, tetraethyl titanate, tetraisopropyl titanate；The acid
Liquid is the aqueous solution of water-soluble organic acid, inorganic acid.
5. the TiO as claimed in claim 32The preparation side of@PZT nano-wire array/polymer composite dielectric material
Method, which is characterized in that in polymer solution, the concentration of polymer is 7~9wt%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710564172.5A CN107275475B (en) | 2017-07-11 | 2017-07-11 | A kind of TiO2@PZT nano-wire array/polymer composite dielectric material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710564172.5A CN107275475B (en) | 2017-07-11 | 2017-07-11 | A kind of TiO2@PZT nano-wire array/polymer composite dielectric material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107275475A CN107275475A (en) | 2017-10-20 |
| CN107275475B true CN107275475B (en) | 2019-07-05 |
Family
ID=60072008
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710564172.5A Active CN107275475B (en) | 2017-07-11 | 2017-07-11 | A kind of TiO2@PZT nano-wire array/polymer composite dielectric material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107275475B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110746185B (en) * | 2019-09-30 | 2021-11-02 | 中国科学院上海硅酸盐研究所 | Titanium oxide nanowire array/lead lanthanum zirconate antiferroelectric composite film material and preparation method thereof |
| CN111646473B (en) * | 2020-06-04 | 2022-02-11 | 松山湖材料实验室 | Si-TiO2Preparation method of-C composite nanowire, product and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102891249A (en) * | 2011-07-20 | 2013-01-23 | 三星电子株式会社 | Electric energy generating device and driving method thereof |
| CN103296922A (en) * | 2012-02-23 | 2013-09-11 | 三星电子株式会社 | Nano-piezoelectric generator and method of manufacturing the same |
-
2017
- 2017-07-11 CN CN201710564172.5A patent/CN107275475B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102891249A (en) * | 2011-07-20 | 2013-01-23 | 三星电子株式会社 | Electric energy generating device and driving method thereof |
| CN103296922A (en) * | 2012-02-23 | 2013-09-11 | 三星电子株式会社 | Nano-piezoelectric generator and method of manufacturing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107275475A (en) | 2017-10-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhang et al. | High discharge energy density at low electric field using an aligned titanium dioxide/lead zirconate titanate nanowire array | |
| KR100726319B1 (en) | Precursor solution, method for manufacturing precursor solution, pztn compound oxide, method for manufacturing pztn compound oxide, piezoelectric element, ink jet printer, ferroelectric capacitor, and ferroelectric memory | |
| CN101717272B (en) | Preparation method of lead zirconate titanate thick film with preferable grain orientation (100) | |
| CN107056087A (en) | A kind of preparation method of the thin dielectric film with titanic oxide nanorod array | |
| CN107275475B (en) | A kind of TiO2@PZT nano-wire array/polymer composite dielectric material and preparation method thereof | |
| KR102330630B1 (en) | Composition for forming manganese- and niobium-doped pzt piezoelectric film | |
| KR20160138417A (en) | Mn-doped pzt-based piezoelectric film formation composition and mn-doped pzt-based piezoelectric film | |
| CN100376506C (en) | Non-plumbum series ferroelectric film with ingredient gradient distribution and its preparation method | |
| CN104877152B (en) | A kind of method for preparing copper-based nano zinc oxide polyvinylidene fluoride composite material | |
| JP6237407B2 (en) | Method for forming Mn and Nb doped PZT piezoelectric film | |
| CN102060529B (en) | Nano Ag particle-Pb(Zr0.52Ti0.48)O3 filtration type composite ceramic film and preparation method thereof | |
| CN100345799C (en) | Bismuth zinc niobate / barium strontium titanate composite dielectric adjustable thick film preparation method | |
| CN101388434B (en) | Preparation of silicium/strontium lanthanum cobaltocyanate/lead zirconate titanate three layer construction ferroelectric material | |
| KR20140118724A (en) | Pzt-based ferroelectric thin film and method of forming the same | |
| CN101074170A (en) | Production of silicon-based zirconium-titanium acid lead-ferroelectric thick film | |
| CN102061460B (en) | Nanometer Ag particle-(Ba0.65, Sr0.35)TiO3 seepage-type composite ceramic film and preparation method thereof | |
| CN115895354B (en) | Multi-layer nano-structure composite dielectric and flexible composite dielectric material, and preparation method and application thereof | |
| CN102176355B (en) | Nano Ag particle-(Pb0.4Sr0.6)TiO3 solid solution seepage-type composite ceramic film and preparation method thereof | |
| Wen et al. | Improving energy storage performance of sol-gel-derived PbZrO3 thin films by adjusting the water/acetic acid solvent ratio | |
| Wang et al. | The effects of ceramic fillers’ performance and preparation process on PZT-based/P (VDF-TrFE) flexible composite films | |
| CN114956812B (en) | Lead titanate-lead zirconate nano composite film and preparation method thereof | |
| CN111978085B (en) | Preparation method of pure lead zirconate titanate nanofiber ceramic material | |
| CN110451954B (en) | Sodium bismuth titanate-based low-lead piezoelectric film with high inverse piezoelectric coefficient and preparation method thereof | |
| Hu et al. | Enhanced dielectric properties of polyvinylidene fluoride nanocomposites via calcium copper titanate nanofibers | |
| CN116234412A (en) | High-electro-strain bismuth sodium titanate-based lead-free piezoelectric film and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |