CN108899415A - A kind of curtain coating-polarization preparation method of flexibility ferro-electricity compound film - Google Patents
A kind of curtain coating-polarization preparation method of flexibility ferro-electricity compound film Download PDFInfo
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
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- 230000010287 polarization Effects 0.000 claims abstract description 66
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- 238000000034 method Methods 0.000 claims abstract description 23
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- 230000008569 process Effects 0.000 claims abstract description 12
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- 239000000463 material Substances 0.000 claims abstract description 9
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- 239000007788 liquid Substances 0.000 claims description 15
- 229910052451 lead zirconate titanate Inorganic materials 0.000 claims description 14
- 239000011521 glass Substances 0.000 claims description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 11
- 238000012545 processing Methods 0.000 claims description 11
- WSMQKESQZFQMFW-UHFFFAOYSA-N 5-methyl-pyrazole-3-carboxylic acid Chemical compound CC1=CC(C(O)=O)=NN1 WSMQKESQZFQMFW-UHFFFAOYSA-N 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 9
- 230000008859 change Effects 0.000 claims description 7
- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 239000000908 ammonium hydroxide Substances 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 6
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- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- XLOFNXVVMRAGLZ-UHFFFAOYSA-N 1,1-difluoroethene;1,1,2-trifluoroethene Chemical group FC(F)=C.FC=C(F)F XLOFNXVVMRAGLZ-UHFFFAOYSA-N 0.000 claims description 2
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- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims description 2
- 229910002113 barium titanate Inorganic materials 0.000 claims description 2
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- 239000010703 silicon Substances 0.000 claims description 2
- OQMIRQSWHKCKNJ-UHFFFAOYSA-N 1,1-difluoroethene;1,1,2,3,3,3-hexafluoroprop-1-ene Chemical compound FC(F)=C.FC(F)=C(F)C(F)(F)F OQMIRQSWHKCKNJ-UHFFFAOYSA-N 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 claims 1
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- XILIYVSXLSWUAI-UHFFFAOYSA-N 2-(diethylamino)ethyl n'-phenylcarbamimidothioate;dihydrobromide Chemical compound Br.Br.CCN(CC)CCSC(N)=NC1=CC=CC=C1 XILIYVSXLSWUAI-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- 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
- H10N30/01—Manufacture or treatment
- H10N30/09—Forming piezoelectric or electrostrictive materials
- H10N30/092—Forming composite materials
-
- 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
- H10N30/01—Manufacture or treatment
- H10N30/04—Treatments to modify a piezoelectric or electrostrictive property, e.g. polarisation characteristics, vibration characteristics or mode tuning
- H10N30/045—Treatments to modify a piezoelectric or electrostrictive property, e.g. polarisation characteristics, vibration characteristics or mode tuning by polarising
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- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
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- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
A kind of curtain coating-polarization preparation method of flexibility ferro-electricity compound film, belongs to power and energy technical field of material.The present invention utilizes and forms electrostatic interaction mechanism present in hydrogen bond, induction PVDF based polyalcohol molecule realizes layer-by-layer electrostatic self-assembled on curtain coating substrate, dipole ordered arrangement realizes self poling in situ in ferroelectric polymers in this self assembling process, then polarization doped ceramics phase is handled by thermal poling, so that ferroelectric polymers phase adulterates the perhaps reverse polarization in the same direction of mutually the two to realize the interference for inhibiting pyroelectricity signal in the interference or piezoelectricity application field of piezoelectric signal in pyroelectricity application field respectively with ferroelectricity.The present invention adjusts one step polarized ferro-electric of direction of an electric field doping phase after only needing casting film-forming without carrying out polarization process twice according to actual needs.Production procedure is simplified, equipment investment is reduced, low in cost, high reliablity, energy consumption is less, is advantageous to promote the industrialized production of flexible ferroelectric polymer film.
Description
Technical field
The invention belongs to functional material preparation technical fields, and in particular to a kind of curtain coating-pole of flexibility ferro-electricity compound film
Change preparation method.
Background technique
Kynoar (PVDF) and its copolymer are a kind of functional materials with piezoelectricity, pyroelectricity and ferroelectric properties,
Such material has many advantages, such as that flexibility, impact resistance, corrosion-resistant, easy processing is integrated, can be used for making pliable pressure temperature integration
Sensor, so bionics skin field technical staff is caused greatly to pay close attention to.However the piezoelectricity of ferroelectric polymers, pyroelectric coefficient
It is usually smaller, ferroelectric ceramics doping is added in ferroelectric polymers thus and mutually forms ferroelectric ceramics/ferroelectric polymers composite wood
Material becomes research mainstream and is concerned.But such Ferroelectric Composites have a major defect, are exactly ferroelectric ceramics/iron
The piezoelectric modulus and pyroelectric coefficient of electric polymer composite material often increase simultaneously, so that poly- using ferroelectric ceramics/ferroelectricity
The pyroelectric detector of compound composite material is being more easier to be interfered by piezoelectric signal in actual work, reduces device performance,
Increase back end signal processing and extracts pyroelectricity signal difficulty；Vice versa, using ferroelectric ceramics/ferroelectric polymers composite material
Piezoelectric detector also has the defect being easy by pyroelectricity signal interference.
It is published within 1999 the article of Applied Physics Letters magazine《Effect of poling
procedure on the properties of lead zirconatetitanate/vinylidene fluoride-
trifluoroethylene composites》(《Polarization process is to lead zirconate titanate/vinylidene-trifluoro-ethylene composite material
The influence of energy》) in report a kind of substep polarization method, specifically based on ferroelectricity doping phase (ferroelectric ceramics or crystal) and PVDF
The piezoelectric modulus symbol of ferroelectric polymers parent phase (i.e. polymeric matrix) the mutually identical principle of pyroelectric coefficient symbol instead, selection
Property enhancing laminated film pyroelectric property or piezoelectric property, i.e., when polymeric matrix and ferroelectricity doping phase polarization direction it is opposite
When, the pyroelectric property of the formed laminated film of the two weakens and piezoelectric property enhances；Conversely, when polymeric matrix and ferroelectricity are mixed
When miscellaneous phase polarization direction is identical, the pyroelectric of the formed laminated film of the two be can increase and piezoelectric property weakens.In this article
Technique is specific as follows：The laminated film for preparing the formation of PZT/ copolymer using compression moulding first, then uses 35MV/m direct current
Field acts on laminated film 1 hour under the conditions of 115 DEG C (Curie temperature TCP that this temperature is greater than polymer), then maintains electricity
Until sample temperature is cooled to room temperature, thus obtained polymer and ceramic phase is polarized and polarization direction is identical is compound
The piezoelectric property of film is suppressed and pyroelectric can be promoted；And in order to enable ceramic phase polarization direction and polymer pole
Change contrary, sample is heated to 50 DEG C again, and then applying intensity at this temperature is 10MV/m and direction and aforementioned behaviour
Make the opposite DC electric field of polarization direction, maintains electric field after acting on laminated film 30 minutes until sample temperature is cooled to room
Temperature, since this applies the coercive electric field that electric field strength is much smaller than polymer, polarization of polymer intensity will be unaffected and ceramic
It meets and is reversed polarization, the pyroelectric property for thus obtaining laminated film is suppressed and piezoelectricity can be promoted.On however,
Stating substep polarization method, there are obvious shortcomings：Because its first step poling parameter in the same direction is actually reported in the literature with other
The thermal poling technique height that thermal discharging composite film commonly uses is identical, but other documents are not reported and observe laminated film
Piezoelectric signal offset or weaken, such as：The article being published in for 1979 on Journal of Applied Physics magazine
《Piezoelectric properties in the composite systems of polymers and PZT
ceramics》(《Piezoelectric property in polymer and PZT composite system》), it is published within 2013 Sensors and Actuators
Article on A《PZT/PVDF composites doped with carbon nanotubes》(《Doped carbon nanometer pipe
PZT/PVDF composite material》And the article being published on Materials magazine in 2017《Effe ct of Polymer
Matrix on the Structure and Electric Properties of Piezoelectric Lead
Zirconatetitanate/Polymer Composites》(《Polymeric matrix is to piezoelectric lead zirconate titanate/polymer composite
Expect the influence of structure and electrical property》).In fact, since the loss of ferroelectric ceramics/ferroelectric polymers laminated film is larger so that thin
Film breakdown voltage is lower, and polarized electric field is generally lower than ferroelectric polymers coercive electric field.Therefore above-mentioned polarization mode in the same direction
Can polarization doping phase, the practical effect for only serving flexible carrier of polymer and fail to polarize, relevant report was referring to aforementioned 1979
Article and the University of Wales doctoral thesis conferred a degree in 1994 being published on Journal of Applied Physics magazine
《Ferroelectric composites for pyro-and piezoelectric applications》(《Ferroelectricity is compound
The pyroelectricity of material, piezoelectricity application》).
Summary of the invention
In view of described above, the present invention in existing ferro-electricity compound film preparation process for, since breakdown potential is forced down, causing
Polymer phase there are problems that being difficult to polarize in laminated film, provide a kind of stream of simple, effective flexible ferro-electricity compound film
Prolong-polarize preparation method.This method is achieved that the self poling in situ of polymer phase during casting film-forming, then imposes again
High pressure mutually carries out thermal poling to adulterating in laminated film, passes through and changes the heat that Selective long-range DEPT laminated film is realized in thermal poling direction
Release electrical property or piezoelectric property.This invention simplifies production procedures, reduce equipment investment, reduce costs, and improve life
Efficiency is produced, commercial introduction is conducive to.
To achieve the goals above, the present invention provides the following technical solutions：
A kind of curtain coating-polarization preparation method of flexibility ferro-electricity compound film, which is characterized in that include the following steps：
Step 1：It prepares ferroelectric polymers and adulterates the mixed solution mutually formed with ferroelectricity, the ferroelectric polymers is PVDF base
Polymer；
Step 2：Hydrophilic treated is carried out to substrate, hydrophilic radical is connected to substrate surface, hydrophilic modifying substrate is made；
Step 3：By mixed solution curtain coating in forming liquid film on the hydrophilic modifying substrate；By controlling casting temperature
Curing process is carried out to the liquid film with the curtain coating time, so that solvent volatilizees in the liquid film, the dipole of polymer phase is made
The ferro-electricity compound film of spontaneous orientations；
Step 4：Thermal poling processing is carried out to the ferro-electricity compound film, the intensity that the thermal poling handles electric field used is small
The coercive electric field of ferroelectric polymers phase in ferro-electricity compound film, so that ferroelectricity doping phase and the iron in ferro-electricity compound film
The polarization direction of electric polymer phase is identical or on the contrary, so far completes the preparation of ferro-electricity compound film.
Further, hydrophilic radical includes hydroxyl, amino or carboxyl in the present invention.
Further, in the present invention hydrophilic treated be specifically the mixed solution for using the concentrated sulfuric acid and hydrogen peroxide to be formed or
The mixed solution that ammonium hydroxide and hydrogen peroxide are formed handles substrate, so that the parents such as substrate surface suspension hydroxyl, amino or carboxyl
Water base group.
Further, substrate should can handle suspension hydrophilic radical, substrate selection warp in the present invention by surface hydrophilic
The glass plate or silicon wafer of polishing treatment.
PVDF based polyalcohol in the present invention, as polyvinylidene fluoride and its copolymer, including but not limited to：Gather inclined difluoro
Ethylene (PVDF), poly- (vinylidene fluoride-trifluoro-ethylene) copolymer [P (VDF-TrFE)] or poly- (vinylidene fluoride-hexafluoro third
Alkene) copolymer [P (VDF-HFP)]
The material of ferroelectricity doping phase of the present invention is preferably lead zirconate titanate, lithium tantalate or barium titanate.
The mass concentration of ferroelectric polymers is 5%~25% in mixed solution of the present invention, and ferroelectricity adulterates the mass concentration of phase
It is 1%~5%.
Liquid film solidify in temperature and time be quality of forming film major influence factors, it is preferred that, the present invention solidification
The process conditions of processing are：Casting temperature is 40 DEG C~60 DEG C, and the curtain coating time is 3 hours~5 hours.
As specific embodiment, uses in the step 4 along substrate normal direction and self-reference substrate side is compound to ferroelectricity
The DC electric field of film side carries out thermal poling processing, so that the piezoelectric property for handling gained ferro-electricity compound film through thermal poling increases
Pyroelectric property inhibition by force.
As specific embodiment, used along substrate normal direction and from ferro-electricity compound film side extremely in the step 4
The DC electric field of substrate side carries out thermal poling processing, so that handling the pyroelectric property of gained ferro-electricity compound film through thermal poling
Enhance and piezoelectric property inhibition.
The principle of the present invention is illustrated in detail below：
By carrying out hydrophilic treated to substrate, so that the hydrophilic radicals such as substrate surface suspension hydroxyl, amino, carboxyl,
Then ferroelectric polymers, ferroelectricity doping are mutually formed finely dispersed mixed solution and are cast and modified in through hydrophilic radical with solvent
Substrate on.Since ferroelectric polymers selects PVDF based polyalcohol, and the F atom in PVDF based polyalcohol is due to electronegativity pole
By force, therefore attracted and close to substrate surface layer and form hydrogen by the hydrophilic radical (hydroxyl, amino, carboxyl etc.) modified on substrate surface
Key.Hydrogen bond is substantially a kind of electrostatic force, and the electrostatic that F atom forms hydrogen bond with substrate surface modification group in ferroelectric polymers draws
Power can drive carbochain in polymer to rotate.And on the one hand this rotation can promote non-ferroelectric phase to the transformation of ferroelectric phase,
Increase the content of ferroelectric phase in film；On the other hand, make the ferroelectric polymer near substrate in the hydrogen bond that substrate surface is formed
According to F atom close to corresponding aligned transfer of the H atom far from substrate side in substrate side in object molecular layer, so that base
Dipole moment produces ordered arrangement in the first layer polymer molecule layer that plate surface is formed.Polarity phase sheet in PVDF based polyalcohol
Body contains dipole, that is, has negatively charged CF2Group and positively charged CH2Group, when first layer molecular ordered arrangement
Afterwards, Self assembly effect is generated, dipole, which is formed, in induction subsequent layers polymer molecule layer similarly aligns,
And then realize the self poling in situ of ferro-electricity compound film.And ferroelectricity doping is mutually dispersed in ferroelectric polymers phase and fails to form orientation
Arrangement, cannot achieve spontaneous polarization, it is therefore desirable to right by applying high pressure (breakdown voltage that field strength is lower than ferro-electricity compound film)
Ferroelectricity doping mutually carries out thermal poling.Polarization field strength is much smaller than the coercive electric field of ferroelectric polymers phase, therefore thermal poling processing is
In order to which polarized ferro-electric adulterates phase.Direction by changing thermal poling can then realize that ferroelectric polymers phase adulterates phase two with ferroelectricity respectively
Person's perhaps reverse polarization in the same direction and then the interference or piezoelectricity application for realizing piezoelectric signal in inhibition pyroelectricity application field respectively
The interference of pyroelectricity signal in field.
Compared with prior art, beneficial effects of the present invention are as follows：
The present invention utilizes hydrogen bond action mechanism, realizes the first layer molecule of the PVDF based polyalcohol parent phase in laminated film
Ordered arrangement, and then the dipole in induced polymer subsequent layers also successively realizes have under the action of electrostatic self-assembled mechanism
Sequence arrangement can either promote non-ferroelectric phase in polymer parent phase to increase in ferro-electricity compound film to the transformation of ferroelectric phase based on this
The content of ferroelectric phase, and dipole ordered arrangement in polymer parent phase is enabled to realize self poling in situ, then by thermoae
Change and handles polarization doped ceramics phase, so that the in the same direction or reverse polarization of both ferroelectric polymers phase and ferroelectricity doping phase, thus point
The interference of pyroelectricity signal in the interference of piezoelectric signal in pyroelectricity application field or piezoelectricity application field Shi Xian not inhibited.This
Conventional iron electricity preparation method of composite film is compared in invention, avoids that the polarizing voltage as needed for ferroelectric polymers is big and ferroelectricity is compound
Small the caused ferroelectric polymers of breakdown voltage of film tolerance is mutually difficult to polarized defect；And the present invention is obtaining ferroelectric polymer
When object phase and ferroelectricity doping phase polarization direction reverse effect, since the present invention realizes the in situ from pole of ferroelectric polymers phase
Change, there is no need to carry out polarization process twice, adjusts one step of direction of an electric field polarization iron according to actual needs after only needing casting film-forming
Electrically doped phase.This invention simplifies production procedures, reduce equipment investment, reliability of technology is high, and energy consumption is less, reduces
Production cost is advantageous to promote the industrialized production of flexible ferroelectric polymer film.
Detailed description of the invention
Fig. 1 is that ferroelectric polymers phase and ferroelectricity doping phase in obtained ferro-electricity compound film are handled through step 3 of the present invention
Dipole is orientated schematic diagram.
Fig. 2 is the ferroelectric polymers phase in the ferro-electricity compound film for using polarization process in the same direction to obtain through step 4 of the present invention
Schematic diagram is orientated with the dipole of ferroelectricity doping phase.
Fig. 3 is the ferroelectric polymers phase in the ferro-electricity compound film for using reverse polarization to handle through step 4 of the present invention
Schematic diagram is orientated with the dipole of ferroelectricity doping phase.
Fig. 4 is the pyroelectric response curve for working as the ferro-electricity compound film that step 4 of the present invention is obtained using polarization process in the same direction
Figure.
Fig. 5 is the piezoelectric response curve graph for working as the ferro-electricity compound film that step 4 of the present invention is handled using reverse polarization.
1 adulterates phase dipole for ferroelectricity in figure, and 2 be ferroelectric polymers phase dipole.
Specific embodiment
The principle of the present invention is further illustrated with reference to the accompanying drawings of the specification：
A kind of curtain coating-polarization preparation method of flexibility ferro-electricity compound film, which is characterized in that include the following steps：
Step 1：The preparation of film forming solution：
Suitable ferroelectric ceramics, the material category of ferroelectric polymers and solvent type are selected according to actual needs；By iron
Electric polymer powder or grain dissolution enter in suitable solvent, stir evenly in a heated condition molten to obtain ferroelectric polymers
Ferroelectric ceramics is dissolved into ultrasonic disperse in suitable solvent by liquid, is then mixed with the ferroelectric polymers solution, under heating condition
It stirs evenly, preparation obtains film forming solution；
Step 2：The hydrophilic treated of substrate；
The substrate will clean, dried is placed in the beaker for filling hydrophilic treated solution, and the beaker is then placed on water
For a period of time, taking-up is cleaned up and is dried with deionized water constant temperature in bath cabinet；
Step 3：Casting film-forming；
Film forming solution curtain coating is formed into liquid film on by the obtained substrate of step 2 processing, by control casting temperature and
The time is cast to liquid film progress curing process, so that solvent volatilizees in film forming solution, so that solidification obtains ferroelectric polymers
The orderly aligned ferro-electricity compound film of phase dipole；
During forming liquid film, since the hydrogen atom of the hydrophilic radical (such as hydroxyl) of substrate surface easily loses outside
Layer electronics and have electropositive, and the ferroelectric polymers that the present invention selects have the very strong fluorine atom of electronegativity, easily obtain electricity
Son and have elecrtonegativity.Therefore ferroelectricity composite solution is in casting film-forming on the substrate modified through hydrophilic radical, ferroelectric polymers
Middle fluorine atom forms hydrogen bond close to substrate and with hydrophilic radical hydroxyl on substrate.And hydrogen bond is substantially a kind of electrostatic attraction,
Carbochain in ferroelectric polymers can be driven to turn under electrostatic attraction effect between hydroxyl and fluorine atom, so that more CF2Base
It rolls into a ball towards on the inside of substrate, and corresponding CH2Group has more ferroelectric polymer moleculars towards substrate outside
TTT conformation (β phase), and the dipole in β phase is realized align on the surface of the substrate.First layer unimolecule ferroelectric polymers
The ordered arrangement of middle dipole further induces dipole in subsequent layers polymer to generate under electrostatic attraction effect successively certainly
Effect is assembled, realizes the spontaneous orientation polarization of entire polymer phase.Fig. 1 show the polarization of ferro-electricity compound film after casting film-forming
State, wherein oriented alignment is presented in ferroelectric polymers phase dipole 2, and ferroelectricity doping 1 confusion of phase dipole is dispersed in numerous iron
Between electric polymer phase dipole 2, disorder distribution is presented.
Step 4：Thermal poling
Ferro-electricity compound film made from step 3 is plated into metal aluminium electrode, with oil bath polarizer apparatus to ferroelectricity doping mutually into
The polarization direction of row electric polarization, DC electric field used in electric polarization should select according to actual needs；When the direction of DC electric field is
When being directed toward substrate-side by ferro-electricity compound film side, ferroelectricity adulterates the spontaneous polarization direction of the polarization direction and ferroelectric polymers phase of phase
It is consistent, as indicated with 2, flexible iron is made in referred to as polarization in the same direction to dipole orientation schematic diagram at this time in ferro-electricity compound film
The piezoelectric signal of electric laminated film is suppressed and pyroelectric property enhances；When the direction of DC electric field is to be directed toward iron by substrate-side
When replying conjunction film side by cable, the polarization direction that ferroelectricity adulterates the polarization direction and ferroelectric polymers phase of phase is exactly the opposite, and ferroelectricity is compound
As indicated at 3, the pyroelectricity of flexible ferro-electricity compound film is made in referred to as reverse polarization to dipole orientation schematic diagram at this time in film
Signal is suppressed and piezoelectric property enhances.
For the ease of becoming apparent from, completely understanding technical solution of the present invention, carry out combined with specific embodiments below detailed
Explanation：
Embodiment 1：
Ultrasonic disperse in n,N-Dimethylformamide (DMF) solvent is added in lithium tantalate (LT) ferroelectric ceramics powder, simultaneously
PVDF (polyvinylidene fluoride) powder is dissolved in DMF solvent, is then mixed two kinds of liquid, being configured to LT mass concentration is
5%, the mixed solution that PVDF mass concentration is 15%, magnetic agitation 2 hours under 60 DEG C of condition of water bath heating keep solute abundant
It is uniformly mixed, obtains mixed solution；
By clean, drying glass substrate be put into fill Piranha solution (volume ratio of the concentrated sulfuric acid and hydrogen peroxide be 7:
3) in beaker, then the beaker is placed in 50 DEG C of constant temperature of water bath constant temperature 1 hour, then takes out glass substrate
It adopts and is washed with deionized water and dries, obtain the glass substrate through hydroxyl modified；
The above-mentioned mixed solution prepared is cast on through the processed glass substrate of Piranha solution, it can by adjusting
The temperature of control heating plate is 40 DEG C and solvent in film is volatilized, and eventually passes through solidification in 4 hours and obtains ferro-electricity compound film；
By above-mentioned ferro-electricity compound film after aluminium electrode is deposited, then (model HYJH-8- is placed into oil bath polarization device
5) thermal poling, is carried out to ferro-electricity compound film, polarizing voltage is set as 20kV, and the thermal poling time is 0.5 hour.Polarizing voltage is low
In the coercivity of ferroelectric polymers phase, ferroelectricity can only be adulterated mutually polarize in this way.Substrate when polarization is connect in the present embodiment
Anode and film connects the obtained ferro-electricity compound film polarized sample of cathode (in the same direction polarization) and is named as A1；Substrate when polarization is connect
Cathode and film connect positive (reverse polarization) obtained ferro-electricity compound film polarized sample and are named as A2.
Infrared laser is emitted using infrared laser, spot diameter φ 3mm controls infrared laser by signal generator
Output power and output frequency be respectively 80mW and 4Hz so that infrared laser vertical irradiation A1, A2 made from the present embodiment
In the top electrode of laminated film.As a result as shown in figure 4, being also as seen from Figure 4 4Hz in the collected signal frequency of oscillograph,
Explanation is pyroelectric response signal.Wherein, the pyroelectricity voltage responsive of A1 film is 3.5V, and the pyroelectricity voltage responsive of A2 film is
1.4V.The pyroelectricity signal of A1 film is much larger than the pyroelectricity signal of A2 film, illustrates that the ferroelectric polymers in laminated film is mutually also right
Pyroelectric response contributes, and otherwise, the pyroelectricity signal of A1 film and A2 film should equal in magnitude and opposite in phase.And in A1 film
Ferroelectric polymers phase adulterates polarization direction mutually having the same with ferroelectricity, and ferroelectric polymers phase mutually has with ferroelectricity doping in A2 film
There is opposite polarization direction.Ferroelectric polymers mutually shows pyroelectric and illustrates that its dipole is not confusing array, but has
Preferred orientation to a certain degree, but this preferred orientation be not outfield it is electropolarized as a result, because outfield lower than its coercivity,
It can not effectively polarize to it, its dipole is caused to arrange along direction of an electric field.Illustrate in preceding working procedure, i.e. THIN COMPOSITE
Dipole after film is cast in polymer phase, which has just formd, to be aligned, so as to cause ferroelectric polymers phase dipole
The formation of spontaneous polarization.
Embodiment 2：
Lithium tantalate (LT) ferroelectric ceramics powder is added to ultrasonic disperse in n,N-dimethylacetamide (DMAc) solvent, together
When P (VDF-TrFE) (Kynoar-trifluoro-ethylene copolymer) powder is dissolved in DMAc solvent, then by two kinds of liquid
Mixing, is configured to the mixed solution that BT mass concentration is 5%, P (VDF-TrFE) mass concentration is 15%, in 60 DEG C of heating water baths
Under the conditions of magnetic agitation 2 hours, be sufficiently mixed solute uniformly, obtain mixed solution；
By clean, drying glass substrate be put into fill Piranha solution (volume ratio of the concentrated sulfuric acid and hydrogen peroxide be 7:
3) in beaker, then the beaker is placed in 50 DEG C of constant temperature of water bath constant temperature 1 hour, then takes out glass substrate
It adopts and is washed with deionized water and dries, obtain the glass substrate through hydroxyl modified；
The above-mentioned mixed solution prepared is cast on through the processed glass substrate of Piranha solution, it can by adjusting
The temperature of control heating plate is 40 DEG C and solvent in film is volatilized, and eventually passes through solidification in 4 hours and obtains ferro-electricity compound film；
By above-mentioned ferro-electricity compound film after aluminium electrode is deposited, then (model HYJH-8- is placed into oil bath polarization device
5) thermal poling mutually, is carried out to ferroelectricity doping in ferro-electricity compound film, polarizing voltage is set as 20kV, and the thermal poling time is 0.5 small
When.Substrate when polarization is connect into anode in the present embodiment and film connects the obtained ferro-electricity compound film of cathode (in the same direction polarization) and polarizes
Sample is named as B1；Substrate when polarization is connect into cathode and film connects positive (reverse polarization) obtained ferro-electricity compound film polarization
Sample is named as B2.
Using the mechanical wave of signal generator control vibration exciter output 2Hz vibration, it is applied to made from the present embodiment
On B1, B2 laminated film, as a result as shown in figure 5, the collected signal frequency of oscillograph as seen from Figure 5, is all 2Hz, explanation
It is piezoelectric signal.The piezoelectric voltage response of B2 film is 3.8V, and the voltage responsive of B1 film is 1.8V.The piezoelectric signal of B2 film is much larger than
The piezoelectric signal of B1 film, illustrating to polarize in the same direction inhibits piezoelectric response and reverse polarization enhancing piezoelectric response.
Embodiment 3：
Ultrasonic disperse in n,N-Dimethylformamide (DMF) solvent is added in lithium tantalate (LT) ferroelectric ceramics powder, simultaneously
PVDF (polyvinylidene fluoride) powder is dissolved in DMF solvent, is then mixed two kinds of liquid, being configured to LT mass concentration is
3%, the mixed solution that PVDF mass concentration is 10%, magnetic agitation 2 hours under 60 DEG C of condition of water bath heating keep solute abundant
It is uniformly mixed, obtains mixed solution；
(100) monocrystalline silicon piece cleaned, dried is put into mixed solution (ammonium hydroxide, dioxygen for filling ammonium hydroxide, hydrogen peroxide and water
The volume ratio of water and water is 1: 2: 7) in beaker, then the beaker being placed in constant temperature 1 in 90 DEG C of constant temperature of water bath small
When, then monocrystalline silicon piece taking-up is adopted and is washed with deionized water and dries, obtains the monocrystalline silicon piece through hydroxyl modified；
The above-mentioned mixed solution prepared is cast on through the processed glass substrate of Piranha solution, it can by adjusting
The temperature of control heating plate is 40 DEG C and solvent in film is volatilized, and eventually passes through solidification in 4 hours and obtains ferro-electricity compound film；
By above-mentioned ferro-electricity compound film after aluminium electrode is deposited, then (model HYJH-8- is placed into oil bath polarization device
5) thermal poling, is carried out to ferro-electricity compound film, polarizing voltage is set as 20kV, and the thermal poling time is 0.5 hour.Polarizing voltage is low
In the coercivity of ferroelectric polymers phase, ferroelectricity can only be adulterated mutually polarize in this way.Substrate when polarization is connect in the present embodiment
Anode and film connects the obtained ferro-electricity compound film polarized sample of cathode (in the same direction polarization) and is named as C1；Substrate when polarization is connect
Cathode and film connect positive (reverse polarization) obtained ferro-electricity compound film polarized sample and are named as C2.
Infrared laser is emitted using infrared laser, spot diameter φ 3mm controls infrared laser by signal generator
Output power and output frequency be respectively 80mW and 2Hz so that infrared laser vertical irradiation C1, C2 made from the present embodiment
In the top electrode of laminated film.The signal frequency of 2Hz is collected in oscillograph, the pyroelectricity voltage responsive of C1 film is 3.2V, C2
The pyroelectricity voltage responsive of film is 1.4V.The pyroelectricity signal of C1 film is much larger than the pyroelectricity signal of C2 film, illustrates to polarize in the same direction
Enhance pyroelectric response and reverse polarization and inhibits pyroelectric response.
Embodiment 4：
Ultrasonic disperse in N-Methyl pyrrolidone (NMP) solvent is added in lead zirconate titanate (PZT) ferroelectric ceramics powder, simultaneously
P (VDF-HFP) (Kynoar-hexafluoropropylene copolymer) powder is dissolved in nmp solvent, is then mixed two kinds of liquid
It closes, the mixed solution that PZT mass concentration is 3%, P (VDF-HFP) mass concentration is 15% is configured to, in 60 DEG C of heating water bath items
Magnetic agitation 2 hours under part, are sufficiently mixed solute uniformly, obtain mixed solution；
(100) monocrystalline silicon piece cleaned, dried is put into mixed solution (ammonium hydroxide, dioxygen for filling ammonium hydroxide, hydrogen peroxide and water
The volume ratio of water and water is 1: 2: 7) in beaker, then the beaker being placed in constant temperature 1 in 90 DEG C of constant temperature of water bath small
When, then monocrystalline silicon piece taking-up is adopted and is washed with deionized water and dries, obtains the monocrystalline silicon piece through hydroxyl modified；
The above-mentioned mixed solution prepared is cast on through the processed glass substrate of Piranha solution, it can by adjusting
The temperature of control heating plate is 60 DEG C and solvent in film is volatilized, and eventually passes through solidification in 4 hours and obtains ferro-electricity compound film；
By above-mentioned ferro-electricity compound film after aluminium electrode is deposited, then (model HYJH-8- is placed into oil bath polarization device
5) thermal poling, is carried out to ferro-electricity compound film, polarizing voltage is set as 20kV, and the thermal poling time is 0.5 hour.Polarizing voltage is low
In the coercivity of ferroelectric polymers phase, ferroelectricity can only be adulterated mutually polarize in this way.Substrate when polarization is connect in the present embodiment
Anode and film connects the obtained ferro-electricity compound film polarized sample of cathode (in the same direction polarization) and is named as D1；Substrate when polarization is connect
Cathode and film connect positive (reverse polarization) obtained ferro-electricity compound film polarized sample and are named as D2.
Using the mechanical wave of signal generator control vibration exciter output 1Hz vibration, it is applied to made from the present embodiment
On D1, D2 laminated film, oscillograph collects the signal frequency of 1Hz, and the piezoelectric voltage response of D2 film is 4.3V, the voltage of D1 film
Response is 2V.The piezoelectric signal of D2 film is much larger than the piezoelectric signal of D1 film, and illustrating to polarize in the same direction inhibits piezoelectric response and reversed pole
Change enhancing piezoelectric response.
The embodiment of the present invention is elaborated in conjunction with attached drawing above, but the invention is not limited to above-mentioned
Specific embodiment, above-mentioned specific embodiment is only schematical, rather than restrictive, the ordinary skill people of this field
Member under the inspiration of the present invention, can also make many in the case where not departing from present inventive concept and claimed range
Deformation, these belong to protection of the invention.
Claims (10)
1. a kind of curtain coating-polarization preparation method of flexibility ferro-electricity compound film, which is characterized in that include the following steps：
Step 1：It prepares ferroelectric polymers and adulterates the mixed solution mutually formed with ferroelectricity, the ferroelectric polymers is the polymerization of PVDF base
Object；
Step 2：Hydrophilic treated is carried out to substrate, hydrophilic radical is connected to substrate surface, hydrophilic modifying substrate is made；
Step 3：By mixed solution curtain coating in forming liquid film on the hydrophilic modifying substrate；Pass through control casting temperature and stream
Curing process is carried out to the liquid film between delay, so that solvent volatilizees in the liquid film, the dipole that polymer phase is made is spontaneous
The ferro-electricity compound film of orientations；
Step 4：Thermal poling processing is carried out to the ferro-electricity compound film, the intensity that the thermal poling handles electric field used is less than iron
The coercive electric field of ferroelectric polymers phase in electric laminated film, so that ferroelectricity doping is mutually poly- with the ferroelectricity in ferro-electricity compound film
The polarization direction of conjunction object phase is identical or on the contrary, so far completes the preparation of ferro-electricity compound film.
2. a kind of curtain coating-polarization preparation method of flexible ferro-electricity compound film according to claim 1, it is characterised in that：
It is thermoae using being carried out along the DC electric field of substrate normal direction and self-reference substrate side to ferro-electricity compound film side in the step 4
Change processing, so that the piezoelectric property for handling gained ferro-electricity compound film through thermal poling enhances and pyroelectric property inhibition.
3. a kind of curtain coating-polarization preparation method of flexible ferro-electricity compound film according to claim 1, it is characterised in that：
It is thermoae using the DC electric field progress along substrate normal direction and from ferro-electricity compound film side to substrate side in the step 4
Change processing, so that the pyroelectric property for handling gained ferro-electricity compound film through thermal poling enhances and piezoelectric property inhibition.
4. a kind of curtain coating-polarization preparation method of flexible ferro-electricity compound film according to claim 1, it is characterised in that：
Hydrophilic radical includes hydroxyl, amino or carboxyl in the step 1.
5. a kind of curtain coating-polarization preparation method of flexible ferro-electricity compound film according to claim 4, it is characterised in that：
Hydrophilic treated is specifically the mixed solution for using the concentrated sulfuric acid and hydrogen peroxide to be formed or ammonium hydroxide and hydrogen peroxide in the step 1
The mixed solution of formation handles substrate.
6. a kind of curtain coating-polarization preparation method of flexible ferro-electricity compound film according to claim 1, it is characterised in that：
The PVDF based polyalcohol includes：Polyvinylidene fluoride (PVDF), poly- (vinylidene fluoride-trifluoro-ethylene) copolymer [P (VDF-
)] or poly- (vinylidene fluoride-hexafluoropropene) copolymer [P (VDF-HFP)] TrFE.
7. a kind of curtain coating-polarization preparation method of flexible ferro-electricity compound film according to claim 1, it is characterised in that：
The material of the ferroelectricity doping phase includes lead zirconate titanate, lithium tantalate or barium titanate.
8. a kind of curtain coating-polarization preparation method of flexible ferro-electricity compound film according to claim 1, it is characterised in that：
The hydrophilic modifying substrate of the step 2 includes glass or silicon wafer.
9. a kind of curtain coating-polarization preparation method of flexible ferro-electricity compound film according to claim 1, it is characterised in that：
The mass concentration of ferroelectric polymers is 5%~25% in the mixed solution of the step 1, and the mass concentration of ferroelectricity doping phase is
1%~5%.
10. a kind of curtain coating-polarization preparation method of flexible ferro-electricity compound film according to claim 1, it is characterised in that：
The process conditions of curing process are in the step 3：Casting temperature is 40 DEG C~60 DEG C, and the curtain coating time is 3 hours~5 hours.
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