CN113314664B - Preparation method of perovskite type piezoelectric solid solution - Google Patents
Preparation method of perovskite type piezoelectric solid solution Download PDFInfo
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- 239000006104 solid solution Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 141
- 239000000243 solution Substances 0.000 claims abstract description 83
- 239000000463 material Substances 0.000 claims abstract description 70
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 45
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000000843 powder Substances 0.000 claims abstract description 21
- JPOXNPPZZKNXOV-UHFFFAOYSA-N bromochloromethane Chemical compound ClCBr JPOXNPPZZKNXOV-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000013078 crystal Substances 0.000 claims abstract description 16
- 238000000137 annealing Methods 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 238000000498 ball milling Methods 0.000 claims abstract description 11
- 238000004528 spin coating Methods 0.000 claims abstract description 11
- 239000000725 suspension Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 21
- RAJISUUPOAJLEQ-UHFFFAOYSA-N chloromethanamine Chemical compound NCCl RAJISUUPOAJLEQ-UHFFFAOYSA-N 0.000 claims description 16
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 claims description 14
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 12
- 239000000758 substrate Substances 0.000 claims description 11
- 238000004090 dissolution Methods 0.000 claims description 10
- 238000001704 evaporation Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 3
- OISMQLUZKQIKII-UHFFFAOYSA-L dichlorocadmium;hydrate Chemical compound O.[Cl-].[Cl-].[Cd+2] OISMQLUZKQIKII-UHFFFAOYSA-L 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 6
- YURIYTWAQHHCKU-UHFFFAOYSA-N NCCl.Br Chemical compound NCCl.Br YURIYTWAQHHCKU-UHFFFAOYSA-N 0.000 claims 1
- 239000007864 aqueous solution Substances 0.000 claims 1
- -1 chloromethyl amine bromine salt Chemical class 0.000 abstract description 30
- 239000012266 salt solution Substances 0.000 abstract 2
- 238000012797 qualification Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N triethylamine Natural products CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 9
- 235000012239 silicon dioxide Nutrition 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 8
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 8
- LOUPRKONTZGTKE-WZBLMQSHSA-N Quinine Chemical compound C([C@H]([C@H](C1)C=C)C2)C[N@@]1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OC)C=C21 LOUPRKONTZGTKE-WZBLMQSHSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 5
- 239000010453 quartz Substances 0.000 description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- 235000001258 Cinchona calisaya Nutrition 0.000 description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 4
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 description 4
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 4
- LOUPRKONTZGTKE-UHFFFAOYSA-N cinchonine Natural products C1C(C(C2)C=C)CCN2C1C(O)C1=CC=NC2=CC=C(OC)C=C21 LOUPRKONTZGTKE-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 239000002798 polar solvent Substances 0.000 description 4
- 239000002861 polymer material Substances 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 229960000948 quinine Drugs 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 150000001449 anionic compounds Chemical group 0.000 description 2
- KPWJBEFBFLRCLH-UHFFFAOYSA-L cadmium bromide Chemical compound Br[Cd]Br KPWJBEFBFLRCLH-UHFFFAOYSA-L 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- 229910001412 inorganic anion Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002892 organic cations Chemical class 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- RWRDLPDLKQPQOW-UHFFFAOYSA-N tetrahydropyrrole Natural products C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- MEWFPYXXOQXVFD-UHFFFAOYSA-N chloromethyl(trimethyl)azanium Chemical compound C[N+](C)(C)CCl MEWFPYXXOQXVFD-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- RJYMRRJVDRJMJW-UHFFFAOYSA-L dibromomanganese Chemical compound Br[Mn]Br RJYMRRJVDRJMJW-UHFFFAOYSA-L 0.000 description 1
- GLUUGHFHXGJENI-UHFFFAOYSA-N diethylenediamine Natural products C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- JUHDUIDUEUEQND-UHFFFAOYSA-N methylium Chemical compound [CH3+] JUHDUIDUEUEQND-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- ZVJHJDDKYZXRJI-UHFFFAOYSA-N pyrroline Natural products C1CC=NC1 ZVJHJDDKYZXRJI-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylene diamine Substances C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 1
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
- H10N30/80—Constructional details
- H10N30/85—Piezoelectric or electrostrictive active materials
- H10N30/852—Composite materials, e.g. having 1-3 or 2-2 type connectivity
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention discloses a preparation method of perovskite type piezoelectric solid solution. Belongs to the technical field of piezoelectric materials, and comprises the following preparation steps: adding bromochloromethane and trimethylamine into an acetonitrile solution to obtain a trimethyl chloromethyl amine bromine salt solution; adding inorganic substances into methanol solution to obtain inorganic substance-containing methanol suspension, stirring and dissolving trimethyl chloromethyl amine bromine salt solution and inorganic substance-containing methanol suspension to obtain TMCM-CdBrCl-containing solution 2 Is evaporated to give TMCM-CdBrCl 2 Colorless blocky crystals; ball milling is carried out to obtain molecular piezoelectric material micro powder; mixing the molecular piezoelectric material micro powder with another part of methanol solution to obtain a methanol clarified solution containing the molecular piezoelectric material micro powder; sucking a methanol clarified solution containing molecular piezoelectric material micro powder, spin-coating to form a film, and then annealing to obtain the piezoelectric material film. The piezoelectric film prepared by the invention has flat surface and high preparation qualification rate.
Description
Technical Field
The invention belongs to the technical field of piezoelectric materials, and relates to a preparation method of a perovskite type piezoelectric solid solution; in particular to a perovskite type piezoelectric solid solution and a preparation method of a piezoelectric film thereof.
Background
The piezoelectric material generates electric energy when being stressed, so that the mutual conversion of mechanical energy and electric energy is realized, and the piezoelectric material is very suitable for different types of sensors. Since the first piezoelectricity found in crystals such as quartz in 1880 p.curie and j.curie, piezoelectric materials have been widely used in a variety of industrial, military and civil products. With the rapid development of modern electronic information technology, the development and exploration of piezoelectric materials with excellent performance become current research hotspots. The molecular ferroelectric has the advantages of adjustable structure, good toughness, low acoustic impedance and the like, and has great potential in the aspects of environment-friendly processing, low cost, biocompatibility and the like. Although molecular ferroelectric materials are expected to make up for the deficiencies of inorganic ferroelectric materials, their development is relatively lagging. Reported in 2017TMCM-CdCl 3 Ferroelectric d of single-component organic-inorganic perovskite molecule in class of compounds 33 The values are higher than barium titanate but still far lower than other inorganic ferroelectric solid solutions. Therefore, it is important to design a molecular ferroelectric material with piezoelectric properties comparable to those of ceramic solid solutions.
Disclosure of Invention
The invention aims to: the invention aims to provide a perovskite type piezoelectric solid solution material: TMCM-CdBrCl 2 (TMCM: trimethyl chloromethyl ammonium) so that the method has a huge application prospect in wearable piezoelectric equipment.
The technical scheme is as follows: the invention relates to a preparation method of a perovskite type piezoelectric solid solution, which comprises the following specific operation steps:
(1.1) adding bromochloromethane and trimethylamine into acetonitrile solution at 25 ℃ for ultrasonic dissolution to obtain trimethyl chloromethyl amine bromide solution for later use;
(1.2) adding inorganic matters into methanol solution with the volume fraction of 99.5%, and carrying out ultrasonic treatment to obtain methanol suspension of the inorganic matters;
(1.3) adding the obtained solution of trimethyl chloromethyl amine bromide to the obtained suspension of inorganic matter-containing methanol, and stirring for dissolving to obtain TMCM-CdBrCl-containing solution 2 Methanol clear solution of (a);
will obtain a catalyst containing TMCM-CdBrCl 2 Evaporating the clarified methanol solution at 25℃to obtain TMCM-CdBrCl 2 Colorless blocky crystals;
(1.4) TMCM-CdBrCl to be obtained 2 Ball milling is carried out on the colorless blocky crystals to obtain molecular piezoelectric material micro powder;
(1.5) mixing the obtained molecular piezoelectric material micro powder with another part of methanol solution with the volume fraction of 99.5%, and performing ultrasonic treatment to obtain a methanol clarified solution containing the molecular piezoelectric material micro powder;
(1.6) sucking 20. Mu.L of the obtained methanol clarified solution containing the molecular piezoelectric material micro powder, spin-coating the solution on a glass substrate coated with ITO to form a film, thereby obtaining TMCM-CdBrCl 2 A film;
(1.7) for TMCM-CdBrCl obtained 2 And (3) annealing the film to finally obtain the perovskite type piezoelectric solid solution, namely the piezoelectric material film.
Further, in the step (1.1), the mass concentration of the trimethylamine is: 30wt% in water;
the molar ratio of the bromochloromethane to the trimethylamine is 1:1, the volume of the acetonitrile solution is 100ml, and the reaction time for ultrasonic dissolution is 24 hours.
Further, in the step (1.2), the inorganic substance is any one of anhydrous cadmium chloride, cadmium chloride monohydrate or cadmium chloride 5/2 hydrate;
the volume fraction of methanol solution used was 99.5% and was 100ml.
Further, in the step (1.3), the volume of the inorganic substance-containing methanol suspension and the volume of the trimethyl chloromethyl amine bromide solution used were each 100ml.
Further, in the step (1.4), the time for performing the ball milling treatment is two hours.
Further, in the step (1.5), the mass of the fine powder of the molecular piezoelectric material is 50mg, and the volume in the methanol solution with the volume fraction of 99.5% is 1ml.
Further, in step (1.6), the spin-coating was carried out at a rotation speed of 3000rpm for 40 seconds.
Further, the reaction conditions of the annealing treatment are as follows: annealing at 120℃for 30 minutes.
The beneficial effects are that: compared with the prior art, the method adopted by the invention prepares TMCM-CdBrCl 2 The perovskite type piezoelectric solid solution material and the film avoid the high-temperature sintering and high-pressure polarization process in the room temperature process; the piezoelectric response was excellent (d 33 =400-800 pC/N), far super inorganic piezoelectric material BTO (d 33 =105 pC/N, edge [001]Directional polarization), T c Up to 373K; moreover, the molecular material has flexibility, and can utilize chemical strategies such as fluoro-effect and the like to design and regulate corresponding physical and chemical properties.
Drawings
FIG. 1 is a flow chart of the operation of the present invention;
FIG. 2 shows a ferroelectric TMCMCdBrCl of the present invention 2 A temperature rise-fall reversible DSC contrast schematic;
FIG. 3 shows a ferroelectric TMCMCdBrCl according to the invention 2 Is a comparison schematic diagram of the variable-temperature frequency multiplication effect;
FIG. 4 shows a ferroelectric TMCMCdBrCl of the present invention 2 Schematic diagram of epsilon' at 1MHz as a function of temperature;
FIG. 5 shows a ferroelectric TMCMCdBrCl according to the invention 2 Schematic representation of the TGA spectrum (measurement range 0-850 ℃).
Detailed Description
The invention is further described with reference to the drawings and the detailed description below; in the following description, numerous specific details are set forth in order to provide a thorough understanding of the present application, but the present application may be embodied in many other forms than described herein, and similar modifications may be made by those skilled in the art without departing from the spirit of the present application and, therefore, the present application is not limited to the specific implementations disclosed below.
The invention relates to a preparation method of a perovskite type piezoelectric solid solution, which comprises the following specific operation steps:
(1.1) adding bromochloromethane and trimethylamine into acetonitrile solution at 25 ℃ for ultrasonic dissolution to obtain trimethyl chloromethyl amine bromide solution for later use;
(1.2) adding inorganic matters into methanol solution with the volume fraction of 99.5%, and carrying out ultrasonic treatment to obtain methanol suspension of the inorganic matters;
(1.3) adding the obtained solution of trimethyl chloromethyl amine bromide to the obtained suspension of inorganic matter-containing methanol, and stirring for dissolving to obtain TMCM-CdBrCl-containing solution 2 Methanol clear solution of (a);
will obtain a catalyst containing TMCM-CdBrCl 2 Evaporating the clarified methanol solution at 25℃to obtain TMCM-CdBrCl 2 Colorless blocky crystals;
(1.4) TMCM-CdBrCl to be obtained 2 Ball milling is carried out on the colorless blocky crystal to obtain the molecular piezoelectric materialMaterial micro powder;
(1.5) mixing the obtained molecular piezoelectric material micro powder with another part of methanol solution with the volume fraction of 99.5%, and performing ultrasonic treatment to obtain a methanol clarified solution containing the molecular piezoelectric material micro powder;
(1.6) sucking 20. Mu.L of the obtained methanol clarified solution containing the molecular piezoelectric material micro powder, spin-coating the solution on a glass substrate coated with ITO to form a film, thereby obtaining TMCM-CdBrCl 2 A film;
(1.7) for TMCM-CdBrCl obtained 2 And (3) annealing the film to finally obtain the perovskite type piezoelectric solid solution, namely the piezoelectric material film.
Further, in the step (1.1), the mass concentration of the trimethylamine is: 30wt% in water;
the molar ratio of the bromochloromethane to the trimethylamine is 1:1, the volume of the acetonitrile solution is 100ml, and the reaction time for ultrasonic dissolution is 24 hours.
Further, in the step (1.2), the inorganic substance is any one of anhydrous cadmium chloride, cadmium chloride monohydrate or cadmium chloride 5/2 hydrate;
the volume fraction of methanol solution used was 99.5% and was 100ml.
Further, in the step (1.3), the volume of the inorganic substance-containing methanol suspension and the volume of the trimethyl chloromethyl amine bromide solution used were each 100ml.
Further, in the step (1.4), the time for performing the ball milling treatment is two hours.
Further, in the step (1.5), the mass of the fine powder of the molecular piezoelectric material is 50mg, and the volume in the methanol solution with the volume fraction of 99.5% is 1ml.
Further, in step (1.6), the spin-coating was carried out at a rotation speed of 3000rpm for 40 seconds.
Further, the reaction conditions of the annealing treatment are as follows: annealing at 120℃for 30 minutes.
The reagents and raw materials used in this example are commercially available and common products unless otherwise indicated.
A perovskite type piezoelectric solid solution preparation method is characterized in that the selected piezoelectric material is TMCM-CdBrCl 2 (Me 3 NCH 2 ClCdBrCl 2 ) Organic-inorganic hybrid perovskite ferroelectric TMCM-CdBrCl 2 Not only has excellent ferroelectric property, but also has outstanding piezoelectric response;
specifically, a perovskite type molecular ferroelectric material, the general formula of which is ABX 3 Wherein A is an organic cation (1), B is a metal cation (2), X is an inorganic anion (3), wherein A is an organic cation comprising: tetramethyl amine cation, tetramethyl phosphine cation, trimethyl chloromethyl amine cation, trimethyl fluoromethyl amine cation, trimethyl bromomethyl amine cation, trimethyl iodomethyl amine cation, trimethyl difluoromethyl amine cation, trimethyl trifluoromethyl amine cation, trimethyl hydroxylamine cation, trimethyl ethyl cation, trimethyl propyl cation, trimethyl chloroethyl cation, trimethylamine cation, triethylamine cation, tetraethyl amine cation, triethylamine methyl cation, triethylamine chloromethyl cation, triethylamine fluoromethyl cation, triethylamine bromomethyl cation, triethylamine iodomethyl cation, pyrrolidine cation, pyrroline cation, quinuclidine cation, imidazole cation, pyridine cation, aminopyrrolidine cation, aminoquinuclidine cation, piperazine cation or triethylenediamine cation, and the like;
b is a metal cation comprising: cd (cadmium) type 2+ 、Mn 2+ 、Cu 2+ 、Zn 2+ 、Ni 2+ 、Co 2+ 、Fe 2+ 、Cr 2+ 、V 2+ 、Hg 2+ 、Cu + 、Ag + 、Au + 、Al 3+ 、In 2+ 、Sn 2+ 、Pb 2+ 、Sb 3+ 、Bi 3+ 、Na + 、K + 、Rb + 、Cs + 、Mg 2+ 、Ca 2+ 、Sr 2+ Or Ba (Ba) 2+ Etc.;
x is an inorganic anion including: cl – 、Br – 、I – 、SCN – 、N 3– 、ClO 4– 、CN – Or BF 4– Etc.
The invention provides a film preparation process, and provides guidance for the wide-range reference of the film made of the material.
Example 1:
a method for preparing a perovskite-type molecular ferroelectric material, the method comprising the steps of:
(1) Stirring and mixing bromochloromethane and trimethylamine in acetonitrile at 25 ℃ to obtain trimethyl chloromethyl amine bromide;
(2) Adding inorganic cadmium chloride into methanol solution with the volume fraction of 99.5%, and performing ultrasonic dissolution to obtain inorganic solution;
(3) Adding the trimethyl chloromethyl amine bromide obtained in the step (1) into the inorganic substance solution obtained in the step (2), and stirring and dissolving until the solution is clear;
(4) Slowly evaporating the clear solution obtained in the step (3) to obtain TMCM-CdBrCl 2 Colorless blocky crystals.
A method for preparing a thin film of a perovskite-type molecular ferroelectric material, the method comprising the steps of:
(1) The molecular ferroelectric material TMCM-CdBrCl 2 Ball milling the crystal to obtain molecular piezoelectric material micropowder;
(2) Dissolving the molecular piezoelectric material micropowder obtained in the step (1) in an organic polar solvent to saturate the molecular piezoelectric material micropowder;
(3) Dripping the solution on a cleaned substrate, uniformly coating the solution by using a spin coating mode, and removing the solvent in an oven;
(4) Placing the material in the step (3) on a heat table for heating and annealing treatment to finally obtain a uniform piezoelectric material film;
(5) The organic polar solution in step (2) comprises: water, methanol, DMF, ethanol, acetone, petroleum ether, diethyl ether, chloroform, trichloroethylene, formamide, ethylene glycol, methylacetamide, aminoethanol, acetic acid, propanol, butanol, DMSO, acetonitrile, aniline, ethylenediamine, morpholine, pyridine, THF, quinine, toluene, and other organic solvents;
the substrate in the step (2) is silicon dioxide, quartz or polymeric polymer material.
Example 2:
a method for preparing a perovskite-type molecular ferroelectric material, the method comprising the steps of:
(1) Stirring and mixing dichloromethane and trimethylamine in acetonitrile at the temperature of 25 ℃ to obtain trimethyl chloromethyl amine chloride;
(2) Adding inorganic cadmium bromide into methanol solution with the volume fraction of 99.5%, and performing ultrasonic dissolution to obtain inorganic solution;
(3) Adding the trimethyl chloromethyl amine chloride obtained in the step (1) into the inorganic substance solution obtained in the step (2), and stirring and dissolving until the solution is clear;
(4) Slowly evaporating the clarified solution obtained in the step (3) to obtain TMCM-CdBr 2 Cl colorless bulk crystals.
A method for preparing a thin film of a perovskite-type molecular ferroelectric material, the method comprising the steps of:
(1) The molecular ferroelectric material TMCM-CdBr 2 Performing ball milling treatment on Cl crystals to obtain molecular piezoelectric material micro powder;
(2) Dissolving the molecular piezoelectric material micropowder obtained in the step (1) in an organic polar solvent to saturate the molecular piezoelectric material micropowder;
(3) Dripping the solution on a cleaned substrate, uniformly coating the solution by using a spin coating mode, and removing the solvent in an oven;
(4) Placing the material in the step (3) on a heat table for heating and annealing treatment to finally obtain a uniform piezoelectric material film;
(5) The organic polar solution in step (2) comprises: water, methanol, DMF, ethanol, acetone, petroleum ether, diethyl ether, chloroform, trichloroethylene, formamide, ethylene glycol, methylacetamide, aminoethanol, acetic acid, propanol, butanol, DMSO, acetonitrile, aniline, ethylenediamine, morpholine, pyridine, THF, quinine, toluene, and other organic solvents;
the substrate in the step (2) is silicon dioxide, quartz or polymeric polymer material.
Example 3:
a method for preparing a perovskite-type molecular ferroelectric material, the method comprising the steps of:
(1) Stirring and mixing dichloromethane and trimethylamine in acetonitrile at the temperature of 25 ℃ to obtain trimethyl chloromethyl amine chloride;
(2) Adding inorganic manganese bromide into methanol solution with the volume fraction of 99.5%, and performing ultrasonic dissolution to obtain inorganic solution;
(3) Adding the trimethyl chloromethyl amine chloride obtained in the step (1) into the inorganic substance solution obtained in the step (2), and stirring and dissolving until the solution is clear;
(4) Slowly evaporating the clarified solution obtained in the step (3) to obtain TMCM-MnBr 2 Cl crystals.
A method for preparing a thin film of a perovskite-type molecular ferroelectric material, the method comprising the steps of:
(1) The molecular ferroelectric material TMCM-MnBr 2 Performing ball milling treatment on Cl crystals to obtain molecular piezoelectric material micro powder;
(2) Dissolving the molecular piezoelectric material micropowder obtained in the step (1) in an organic polar solvent to saturate the molecular piezoelectric material micropowder;
(3) Dripping the solution on a cleaned substrate, uniformly coating the solution by using a spin coating mode, and removing the solvent in an oven;
(4) Placing the material in the step (3) on a heat table for heating and annealing treatment to finally obtain a uniform piezoelectric material film;
(5) The organic polar solution in step (2) comprises: water, methanol, DMF, ethanol, acetone, petroleum ether, diethyl ether, chloroform, trichloroethylene, formamide, ethylene glycol, methylacetamide, aminoethanol, acetic acid, propanol, butanol, DMSO, acetonitrile, aniline, ethylenediamine, morpholine, pyridine, THF, quinine, toluene, and other organic solvents;
the substrate in the step (2) is silicon dioxide, quartz or polymeric polymer material.
Example 4:
a method for preparing a perovskite-type molecular ferroelectric material, the method comprising the steps of:
(1) Stirring and mixing bromochloromethane and trimethylamine in acetonitrile at 25 ℃ to obtain trimethyl chloromethyl amine bromide;
(2) Adding inorganic manganese chloride into a methanol solution with the volume fraction of 99.5%, and performing ultrasonic dissolution to obtain an inorganic solution;
(3) Adding the trimethyl chloromethyl amine bromide obtained in the step (1) into the inorganic substance solution obtained in the step (2), and stirring and dissolving until the solution is clear;
(4) Slowly evaporating the clarified solution obtained in step (3) to obtain TMCM-MnBrCl 2 And (5) a crystal.
A method for preparing a thin film of a perovskite-type molecular ferroelectric material, the method comprising the steps of:
(1) The molecular ferroelectric material TMCM-MnBrCl 2 Ball milling the crystal to obtain molecular piezoelectric material micropowder;
(2) Dissolving the molecular piezoelectric material micropowder obtained in the step (1) in an organic polar solvent to saturate the molecular piezoelectric material micropowder;
(3) Dripping the solution on a cleaned substrate, uniformly coating the solution by using a spin coating mode, and removing the solvent in an oven;
(4) Placing the material in the step (3) on a heat table for heating and annealing treatment to finally obtain a uniform piezoelectric material film;
(5) The organic polar solution in step (2) comprises: water, methanol, DMF, ethanol, acetone, petroleum ether, diethyl ether, chloroform, trichloroethylene, formamide, ethylene glycol, methylacetamide, aminoethanol, acetic acid, propanol, butanol, DMSO, acetonitrile, aniline, ethylenediamine, morpholine, pyridine, THF, quinine, toluene, and other organic solvents;
the substrate in the step (2) is silicon dioxide, quartz or polymeric polymer material.
Claims (8)
1. The preparation method of the perovskite type piezoelectric solid solution is characterized by comprising the following specific operation steps:
(1.1) adding bromochloromethane and trimethylamine into acetonitrile solution at 25 ℃ for ultrasonic dissolution to obtain trimethyl chloromethyl amine bromide solution for later use;
(1.2) adding inorganic matters into methanol solution with the volume fraction of 99.5%, and carrying out ultrasonic treatment to obtain methanol suspension of the inorganic matters;
wherein the inorganic matter is any one of anhydrous cadmium chloride, cadmium chloride monohydrate or cadmium chloride 5/2 hydrate;
(1.3) adding the obtained solution of trimethyl chloromethyl amine bromide to the obtained suspension of inorganic matter-containing methanol, and stirring for dissolving to obtain TMCM-CdBrCl-containing solution 2 Methanol clear solution of (a);
will obtain a catalyst containing TMCM-CdBrCl 2 Evaporating the clarified methanol solution at 25℃to obtain TMCM-CdBrCl 2 Colorless blocky crystals;
(1.4) TMCM-CdBrCl to be obtained 2 Ball milling is carried out on the colorless blocky crystals to obtain molecular piezoelectric material micro powder;
(1.5) mixing the obtained molecular piezoelectric material micro powder with another part of methanol solution with the volume fraction of 99.5%, and performing ultrasonic treatment to obtain a methanol clarified solution containing the molecular piezoelectric material micro powder;
(1.6) sucking 20. Mu.L of the obtained methanol clarified solution containing the molecular piezoelectric material micro powder, spin-coating the solution on a glass substrate coated with ITO to form a film, thereby obtaining TMCM-CdBrCl 2 A film;
(1.7) for TMCM-CdBrCl obtained 2 And (3) annealing the film to finally obtain the piezoelectric material film, namely the perovskite type piezoelectric solid solution.
2. The method for producing a perovskite-type piezoelectric solid solution according to claim 1, wherein,
in the step (1.1), the trimethylamine is a 30wt% aqueous solution of trimethylamine in water,
the molar ratio of the bromochloromethane to the trimethylamine is 1:1, the volume of the acetonitrile solution is 100ml, and the reaction time for ultrasonic dissolution is 24 hours.
3. The method for producing a perovskite-type piezoelectric solid solution according to claim 1, wherein,
in step (1.2), the volume fraction of methanol solution used was 100ml.
4. The method according to claim 1, wherein in the step (1.3), the volume of the inorganic substance-containing methanol suspension and the volume of the trimethyl chloromethylamine bromide solution are each 100ml.
5. The method for producing a perovskite-type piezoelectric solid solution according to claim 1, wherein,
in the step (1.4), the time for performing the ball milling treatment is two hours.
6. The method for producing a perovskite-type piezoelectric solid solution according to claim 1, wherein,
in the step (1.5), the mass of the molecular piezoelectric material micro powder is 50mg, and the volume of the methanol solution with the volume fraction of 99.5% is 1ml.
7. The method for producing a perovskite-type piezoelectric solid solution according to claim 1, wherein,
in step (1.6), the spin-coating was carried out at a rotational speed of 3000rpm for 40 seconds.
8. The method for producing a perovskite-type piezoelectric solid solution according to claim 1, wherein,
the reaction conditions of the annealing treatment are as follows: annealing at 120℃for 30 minutes.
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