CN101471180A - Production method for ternary ferroelectric polymer thin-film material - Google Patents
Production method for ternary ferroelectric polymer thin-film material Download PDFInfo
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Abstract
The invention discloses a preparing process of ternary ferroelectric polymer film material, which comprises preparing a precursor solution by using dimethyl sulfoxide as solvent and ternary polymer P (VDF-TrFE-CFE) as solute, and adopting horizontal dipping method to create films and heat-treat films on LB devices, thereby obtaining polymer films which are characterized by controllable nanometer scale, ordered arrangement level and high crystallinity. The film material processed according to the method provides a platform for studying the origin of relaxation ferroelectricity. The P (VDF-TrFE-CFE) ternary ferroelectric polymer films have the properties for studying practical energy memory devices.
Description
Technical field
The present invention relates to ferroelectric polymer thin-film material, be meant a kind of employing Lang Gemiuer (Langmuir-Blodgett, LB) preparation method of the high-energy-density ternary ferroelectric polymer thin-film material of technology growth especially.
Background technology
Organic film condenser market is huge, and need nearly hundred billion every year, and also increasing as the capacitor market of dielectric material with polyvinylidene fluoride (being called for short PVDF).The copolymer of polyvinylidene fluoride and trifluoro-ethylene is called for short: P (VDF-TrFE), it is a kind of good ferroelectric material, except as traditional electric heating modulator material, therefore this polymeric material can be used for preparing the s energy storage capacitor with broad prospect of application because have characteristics such as energy density height, the height of anti-the breakdown electric field.There is report that a kind of chlorine fluoroethylene polymer (PCFE) is introduced recently and forms ter-polymers P (VDF-TrFE-CFE) among the P (VDF-TrFE), the intrinsic ferroelectric polymers is transformed into the relaxation property ferroelectric polymers, thereby improved polymer properties greatly, see B.Chu etc., Science, 313,334 (2006).The origin mechanism of this relaxation behavior is still indeterminate, further improve performance, it must be understood that the physical origin of this relaxor ferroelectric characteristic.
Russia and a joint study group of the U.S. have utilized LB technology growth P (VDF-TrFE) thin-film material, this film can control to only has two molecular layers also to have ferroelectric properties, and thickness only is about 1nm, sees Nature such as A.V.Bune, 391,874 (1998).This LB_P (VDF-TrFE) film shows very large anti-breakdown electric field and energy density.With respect to the polymer thin-film material that conventional method obtains, the LB film of this P (VDF-TrFE) has the characteristics of height molecules align, high-crystallinity, provides very favorable condition for studying some basic physical problems like this.
Because relaxation behavior is relevant with the domain structure of polarization nanometer, therefore, the LB film has been created condition for the research relaxation behavior.On the other hand, polymer LB film can reduce dielectric loss by improving film performance, significantly improves the anti-breakdown electric field and the energy density of film.Therefore, if adopt LB technology growth ternary P (VDF-TrFE-CFE) ferroelectric polymer film, controlling membrane structure on nanoscale, thereby obtain arranging degree of order height, thin polymer film that degree of crystallinity is high, will be of great practical value.But the report that adopts LB technology growth P (VDF-TrFE-CFE) ternary ferroelectric polymer film is not arranged as yet at present.
Summary of the invention
Purpose of the present invention will propose a kind of P (VDF-TrFE-CFE) ternary ferroelectric polymer growth for Thin Film method of controlling exactly on molecular level, provide high performance material for deeply understanding ferroelectric polymers relaxation behavior origin mechanism.
P of the present invention (VDF-TrFE-CFE) ternary ferroelectric polymer growth for Thin Film adopts the LB technology, and its process is:
The preparation of 1 precursor solution
Solvent is dimethyl sulfoxide (DMSO) (being called for short DMSO), and solute is ready-made ter-polymers P (VDF-TrFE-CFE) on sale, and solvent is 100-200ml:0.01-0.02 gram with the solute ratio.Preparation procedure is: take by weighing a certain amount of P (VDF-TrFE-CFE), transfer in one 250 ml flasks, add DMSO, stirred 3-5 hours down at 50-80 ℃, be cooled to room temperature.
The growth of 2 thin-film materials
Adopt LB film growth system P (VDF-TrFE-CFE) the ter-polymers film of growing, method is horizontal czochralski method, the steps include:
§ A extracts precursor solution with syringe, evenly drops in then in the groove that fills deionized water of LB film growth system, places after 1 hour, and precursor solution evenly swims in the surface of deionized water;
The specimen holder that § B will be equipped with substrate then stretches in the groove that fills deionized water, the one side that metal electrode layer is arranged of substrate is contacted with the precursor solution that swims in the deionized water surface, and substrate is lifted under surface pressure 2-5mN/m, obtaining monofilm thickness is between 1-1.5 nanometers.Repeat to lift repeatedly, can obtain the thin-film material of desired thickness.The film that will have substrate at last was 120-140 ℃ of annealing 2-5 hours.Utilize mask plate evaporation Al or Au to the surface of film,, promptly can be used as capacitor and study its electric property as top electrode.
Said substrate is made of at the layer of coating polyimide successively on glass, thermal evaporation growing metal layer glass.Metal level is aluminium or gold, as electrode.
Use P (VDF-TrFE-CFE) the ternary ferroelectric polymer film of method preparation of the present invention, will have following effect:
(a) growth ternary P (VDF-TrFE-CFE) thin polymer film on molecular level, molecules align high-sequential in the film.
(b) P that is grown (VDF-TrFE-CFE) ternary ferroelectric polymer LB film provides material platform for research relaxor ferroelectric origin.
(c) P that is grown (VDF-TrFE-CFE) ternary ferroelectric polymer LB film has the required performance of development of practical energy storage device.
Description of drawings
Fig. 1 is the schematic diagram of the horizontal method growth of LB ternary ferroelectric polymer LB film.
Embodiment
1. the preparation of P (VDF-TrFE-CFE) ternary ferroelectric polymer precursor solution
Take by weighing 0.01g ter-polymers P (60%VDF-33%TrFE-7%CFE) in a 250ml flask, add the 100ml dimethyl sulfoxide (DMSO), stirred 3 hours down, place after 24 hours at 60 ℃, stand-by.
2. horizontal method growth ternary ferroelectric polymer LB film
Get precursor solution 4ml with syringe, evenly drop in the filling in the deionization tank of Nima311D type LB film growth system then, place after 1 hour, the one side that metal A l electrode layer is arranged of glass substrate is contacted with the precursor solution that swims in the deionized water surface, at horizontal transfer film under the surface pressure 5mN/m to the Al electrode layer, lift repeatedly 30 times, then film is placed baking oven 125 ℃ of annealing 5 hours, obtain film thickness at last between 40-50nm, evaporate the Al film more thereon, as top electrode, promptly can be used as capacitor and study its electric property.
Claims (2)
1. the preparation method of a ternary ferroelectric polymer thin-film material is characterized in that concrete steps are as follows:
The preparation of § A precursor solution
Solvent is a dimethyl sulfoxide (DMSO), and solute is ready-made ter-polymers P (VDF-TrFE-CFE) on sale, and solvent is 100-200ml:0.01-0.02 gram with the solute ratio, and preparation procedure is:
Take by weighing a certain amount of P (VDF-TrFE-CFE), transfer in one 250 ml flasks, add dimethyl sulfoxide (DMSO), stirred 3-5 hours down at 50-80 ℃, it is stand-by to be cooled to room temperature;
The growth of § B thin-film material
Adopt LB film growth system P (VDF-TrFE-CFE) the ter-polymers film of growing, the steps include:
§ a extracts precursor solution with syringe, evenly drops in then in the groove that fills deionized water of LB film growth system, places after 1 hour, and precursor solution evenly swims in the surface of deionized water;
The specimen holder that § b will be equipped with substrate then stretches in the groove that fills deionized water, the one side that metal electrode layer is arranged of substrate is contacted with the precursor solution that swims in the deionized water surface, and substrate is lifted under surface pressure 2-5mN/m, obtaining monofilm thickness is between 1-1.5 nanometers, repeat to lift repeatedly, obtain the thin-film material of desired thickness; The thin-film material that will have substrate was at last annealed 2-5 hours down at 120-140 ℃; Utilize mask plate evaporation Al or Au surface, as top electrode to film.
2. according to the preparation method of a kind of high-energy-density ternary ferroelectric polymer thin-film material of claim 1, it is characterized in that: said substrate is made of at the layer of coating polyimide successively on glass, thermal evaporation growing metal layer glass; Metal level is aluminium or gold, as bottom electrode.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102003998A (en) * | 2010-09-17 | 2011-04-06 | 中国科学院上海技术物理研究所 | High-sensitivity uncooled infrared detector |
| CN102632675A (en) * | 2012-04-17 | 2012-08-15 | 电子科技大学 | Method for preparing nanocomposite dielectric film |
| CN103848644A (en) * | 2014-01-17 | 2014-06-11 | 中国科学院上海技术物理研究所 | Preparation method for silver nanoparticle-doped P(VDF-TrFE) (polyvinylidene fluoride-trifluoroethylene) composite thin film |
| CN104194024A (en) * | 2014-08-16 | 2014-12-10 | 复旦大学 | Method for treatment of ferroelectric polymer film by virtue of solvent steam |
| CN104409626A (en) * | 2014-10-16 | 2015-03-11 | 中国科学院上海技术物理研究所 | Preparation method for polyvinylidene fluoride (PVDF)-based high voltage coefficient thin film |
| CN105121538A (en) * | 2013-04-18 | 2015-12-02 | 国立里昂应用科学学院 | Method for manufacturing composite material which is polarizable under the action of a weak electric field |
| CN105283945A (en) * | 2013-04-19 | 2016-01-27 | 阿肯马法国公司 | Ferroelectric memory device |
| CN107065661A (en) * | 2017-03-27 | 2017-08-18 | 上海师范大学 | A kind of equipment for extracting gas-liquid interface film |
| CN110243867A (en) * | 2019-04-28 | 2019-09-17 | 浙江工业大学 | Integrate the flexible intelligent device and its manufacturing method of driving sensing |
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2007
- 2007-12-28 CN CNA2007101735109A patent/CN101471180A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102003998B (en) * | 2010-09-17 | 2011-11-30 | 中国科学院上海技术物理研究所 | High-sensitivity uncooled infrared detector |
| CN102003998A (en) * | 2010-09-17 | 2011-04-06 | 中国科学院上海技术物理研究所 | High-sensitivity uncooled infrared detector |
| CN102632675A (en) * | 2012-04-17 | 2012-08-15 | 电子科技大学 | Method for preparing nanocomposite dielectric film |
| CN102632675B (en) * | 2012-04-17 | 2014-07-16 | 电子科技大学 | Method for preparing nanocomposite dielectric film |
| CN105121538A (en) * | 2013-04-18 | 2015-12-02 | 国立里昂应用科学学院 | Method for manufacturing composite material which is polarizable under the action of a weak electric field |
| CN105121538B (en) * | 2013-04-18 | 2018-04-24 | 国立里昂应用科学学院 | It is used to prepare the method for polarizable composite material under the action of weak electric field |
| CN105283945A (en) * | 2013-04-19 | 2016-01-27 | 阿肯马法国公司 | Ferroelectric memory device |
| CN103848644A (en) * | 2014-01-17 | 2014-06-11 | 中国科学院上海技术物理研究所 | Preparation method for silver nanoparticle-doped P(VDF-TrFE) (polyvinylidene fluoride-trifluoroethylene) composite thin film |
| CN104194024B (en) * | 2014-08-16 | 2017-12-19 | 复旦大学 | The method that solvent vapour handles ferroelectric polymer film |
| CN104194024A (en) * | 2014-08-16 | 2014-12-10 | 复旦大学 | Method for treatment of ferroelectric polymer film by virtue of solvent steam |
| CN104409626A (en) * | 2014-10-16 | 2015-03-11 | 中国科学院上海技术物理研究所 | Preparation method for polyvinylidene fluoride (PVDF)-based high voltage coefficient thin film |
| CN107065661A (en) * | 2017-03-27 | 2017-08-18 | 上海师范大学 | A kind of equipment for extracting gas-liquid interface film |
| CN110243867A (en) * | 2019-04-28 | 2019-09-17 | 浙江工业大学 | Integrate the flexible intelligent device and its manufacturing method of driving sensing |
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