CN106009009B - A kind of preparation method of organic ferroelectric thin film with high polarization intensity - Google Patents
A kind of preparation method of organic ferroelectric thin film with high polarization intensity Download PDFInfo
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- 239000010409 thin film Substances 0.000 title claims abstract description 21
- 230000010287 polarization Effects 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 39
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910003781 PbTiO3 Inorganic materials 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000000758 substrate Substances 0.000 claims abstract description 12
- 239000010408 film Substances 0.000 claims abstract description 8
- 239000000725 suspension Substances 0.000 claims abstract description 7
- 238000004528 spin coating Methods 0.000 claims abstract description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000002086 nanomaterial Substances 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 238000002525 ultrasonication Methods 0.000 abstract 1
- 230000005621 ferroelectricity Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000001341 grazing-angle X-ray diffraction Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000003306 harvesting Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- -1 hydrogen furans Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000131 polyvinylidene Polymers 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2327/16—Homopolymers or copolymers of vinylidene fluoride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
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- Engineering & Computer Science (AREA)
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Abstract
The preparation method of organic ferroelectric thin film disclosed by the invention with high polarization intensity, with PbTiO3PVDF-TrFE is dissolved in tetrahydrofuran by nanometer sheet and PVDF-TrFE first as primary raw material, and suitable PbTiO is then added3Nanometer sheet obtains suspension；By ultrasonication, make PbTiO3Nanometer sheet is homogeneously dispersed in solution, homogeneous film formation in clean substrate is spin-coated on using the method for spin coating, then be heat-treated at 180 DEG C.Preparation process of the present invention is simple, process is easily controllable, and prepared organic ferroelectric thin film has the micro-nano structure of orientation, while also having excellent electric property, and residual polarization is up to 12.4 μ C/cm2。
Description
Technical field
The present invention relates to a kind of preparation methods of organic ferroelectric thin film, belong to organic ferroelectricity polymeric material field.
Background technique
Traditional ceramic material has very high ferroelectric remnant polarization, but preparation process is complicated, brittle and ferroelectricity is damaged
It consumes larger.Organic polymer flexibility is good, f-e loss is low and easy to process.PVDF-TrFE(polyvinylidene fluoride-trifluoro second
Alkene) it is used as a kind of organic ferroelectricity to can be widely applied to energy capture device, pyroelectric infrared detector and non-volatile holographic storage
Device etc. has excellent electric property and wide application prospect.Compared with traditional inorganic Perovskite Phase ferroelectric material,
Lower (the 6 μ C/cm of the residual polarization of PVDF-TrFE2Left and right), its application on electronic device material is limited, therefore, is led to
It crosses distinct methods to be modified PVDF-TrFE, improves its electric property (dielectric, ferroelectricity, piezoelectricity, pyroelectric property etc.), it can
Further to widen the application field of PVDF-TrFE.
The spontaneous polarization strength of PVDF-TrFE is close to 6 μ C/cm2, ferroelectricity coefficient d 33 at room temperature is about -38pm/V,
And due to its fabulous bio-compatibility, there is very big potential using value in terms of energy harvesting and bio-sensing.Mesh
It is preceding to have the methods of a nanometer confinement method, polar solvent method, template, epitaxial growth to the study on the modification for having PVDF-TrFE, but this
Although a little methods can control the orientation of structure to a certain extent, its electric property is not improved very much.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation methods of organic ferroelectric thin film with high polarization intensity.
Organic ferroelectric thin film preparation method with high polarization intensity of the invention, comprising the following steps:
1) substrate is sequentially placed into deionized water, acetone, be cleaned by ultrasonic in dehydrated alcohol, dried；
2) PVDF-TrFE is dissolved in tetrahydrofuran, obtains the tetrahydrofuran solution of PVDF-TrFE, PVDF-TrFE and four
The mass/volume ratio of hydrogen furans is 1/20；
3) by PbTiO3Nanometer sheet is placed in the tetrahydrofuran solution of the resulting PVDF-TrFE of step 2, PbTiO3Nanometer
The mass/volume ratio of the tetrahydrofuran solution of piece and PVDF-TrFE is 0.2%-5.0%, and stirring obtains suspension；
4) sonicating step 3) resulting suspension, make PbTiO3Nanometer sheet is evenly dispersed in PVDF-TrFE's
In tetrahydrofuran solution, after standing 20-40 min, it is spun to using the method for spin coating in clean substrate, obtains film；
5) the obtained film vacuum of step 4) is dry, in 180 DEG C of heat treatment 0.5-2h.
In the present invention, the substrate can be ITO or Si substrate.
In the present invention, the tetrahydrofuran, acetone, dehydrated alcohol purity be not less than chemistry it is pure.
In the present invention, the PbTiO3Nanometer sheet is monocrystalline one-domain structure.
The PbTiO of monocrystalline one-domain structure3Nanometer sheet can refer to Zhejiang University's doctoral thesis --- " perovskite ferroelectric oxide
The adjusting and controlling growth of nanostructure, microstructure and properties research, author are paper money spring English " preparation method acquisition.
Preparation process of the present invention is simple, process is easily controllable, and the thickness of film is related with time of repose and spin coating parameters, institute
Organic ferroelectric film thickness of preparation has the micro-nano structure of orientation at 0.8 μm -1 μm, while also having excellent electrical property
Can, residual polarization is up to 12.4 μ C/cm2。
Detailed description of the invention
Fig. 1 is the glancing incidence XRD spectrum of organic ferroelectric thin film prepared by example 1；
Fig. 2 is the GIWAXS figure of organic ferroelectric thin film prepared by example 1；
Fig. 3 is the AFM figure of organic ferroelectric thin film prepared by example 1；
Fig. 4 is the ferroelectric properties figure of organic ferroelectric thin film prepared by example 1.
Specific embodiment
The present invention is further illustrated with reference to embodiments.
Embodiment 1
1) ITO substrate is successively cleaned by ultrasonic in deionized water, acetone, dehydrated alcohol, is then dried using infrared lamp；
2) PVDF-TrFE of 1g is dissolved in 20 mL tetrahydrofurans, obtains the tetrahydrofuran solution of PVDF-TrFE；
3) by the PbTiO of 0.002g3Nanometer sheet is placed in the resulting solution of step 2, PbTiO3Nanometer sheet and PVDF-
The mass/volume ratio of the tetrahydrofuran solution of TrFE is 0.2%, and stirring obtains suspension；
4) sonicating step 3) resulting suspension, make PbTiO3Nanometer sheet is evenly dispersed in PVDF-TrFE's
In tetrahydrofuran solution, after standing 20 min, by its spin coating, (1500 rpm, 30, s) in clean ITO substrate, are obtained thin
Film；
5) the obtained film vacuum of step 4) is dry, in 180 DEG C of heat treatment 1h.
Organic ferroelectric thin film prepared by this example with a thickness of 0.8 μm, glancing incidence XRD spectrum is shown in Fig. 1, GIWAXS
It is illustrated in Fig. 2, by Fig. 1, Fig. 2 as it can be seen that organic ferroelectric thin film has the micro-nano structure of orientation.AFM is illustrated in Fig. 3, can by Fig. 3
See, obtained organic ferroelectric thin film is made of the rhabdolith of well-crystallized.It is tested by the ferroelectricity tester of Radiant, iron
Electrical property is illustrated in Fig. 4, and residual polarization is 12.4 μ C/cm as seen from the figure2。
Embodiment 2
Specific processing step is same as Example 1, and difference is the weighed PbTiO of step 3)3Nanometer sheet is 0.005g
, PbTiO3The mass/volume ratio of the tetrahydrofuran solution of nanometer sheet and PVDF-TrFE is 0.5%, and step 4) time of repose is 40
Min, step 5) heat treatment time are 0.5 hour.The residual polarization of organic ferroelectric thin film prepared by this example is 10 μ C/cm2。
Embodiment 3
Specific processing step is same as Example 1, and difference is: using Si substrate, the weighed PbTiO of step 3)3It receives
Rice piece is 0.0527g, PbTiO3The mass/volume ratio of the tetrahydrofuran solution of nanometer sheet and PVDF-TrFE is 5.0%, step
4) time of repose is 30 min, and step 5) heat treatment time is 2 hours, the residual polarization of organic ferroelectric thin film prepared by this example
For 8 μ C/cm2。
Claims (4)
1. a kind of organic ferroelectric thin film preparation method with high polarization intensity, it is characterised in that the following steps are included:
1) substrate is sequentially placed into deionized water, acetone, be cleaned by ultrasonic in dehydrated alcohol, dried；
2) PVDF-TrFE is dissolved in tetrahydrofuran, obtains the tetrahydrofuran solution of PVDF-TrFE, PVDF-TrFE and tetrahydro furan
The mass/volume ratio muttered is 1/20；
3) by PbTiO3Nanometer sheet is placed in the tetrahydrofuran solution of the resulting PVDF-TrFE of step 2, PbTiO3Nanometer sheet with
The mass/volume ratio of the tetrahydrofuran solution of PVDF-TrFE is 0.2%-5.0%, and stirring obtains suspension；
4) sonicating step 3) resulting suspension, make PbTiO3Nanometer sheet is evenly dispersed in the tetrahydro of PVDF-TrFE
In tetrahydrofuran solution, after standing 20-40 min, it is spun to using the method for spin coating in clean substrate, obtains film；
5) the obtained film vacuum of step 4) is dry, in 180 DEG C of heat treatment 0.5-2h.
2. the preparation method of organic ferroelectric thin film according to claim 1 with high polarization intensity, it is characterized in that described
Substrate be ITO or Si substrate.
3. the preparation method of organic ferroelectric thin film according to claim 1 with high polarization intensity, it is characterized in that described
PbTiO3Nanometer sheet is monocrystalline one-domain structure.
4. the preparation method of organic ferroelectric thin film according to claim 1 with high polarization intensity, it is characterized in that described
Tetrahydrofuran, acetone, dehydrated alcohol purity be not less than chemistry it is pure.
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| CN106967009B (en) * | 2017-03-28 | 2020-08-07 | 广东工业大学 | Borate ferroelectric film, preparation method and application thereof |
| CN108948390A (en) * | 2018-07-24 | 2018-12-07 | 电子科技大学 | A kind of step curtain coating preparation method of PVDF based polymer film |
| CN108899415B (en) * | 2018-07-24 | 2019-11-01 | 电子科技大学 | A kind of curtain coating-polarization preparation method of flexibility ferro-electricity compound film |
| CN109972136B (en) * | 2019-03-26 | 2020-09-04 | 浙江大学 | Preparation method of oriented growth P (VDF-TrFE) film |
| CN112641534A (en) * | 2020-11-15 | 2021-04-13 | 南京大学 | Near-infrared super-vision flexible artificial retina and manufacturing method thereof |
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