CN113314664B - Preparation method of perovskite type piezoelectric solid solution - Google Patents

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

A kind of preparation method of perovskite type piezoelectric solid solution

technical field

The invention belongs to the technical field of piezoelectric materials, and relates to a preparation method of a perovskite piezoelectric solid solution; in particular, it relates to a preparation method of a perovskite piezoelectric solid solution and a piezoelectric thin film.

Background technique

Piezoelectric materials generate electrical energy when they are stressed, thereby realizing mutual conversion of mechanical energy and electrical energy, so they are very suitable for different types of sensors. Since P. Curie and J. Curie first discovered piezoelectricity in crystals such as quartz in 1880, piezoelectric materials have been widely used in various industrial, military and civilian products. With the rapid development of modern electronic information technology, the development and exploration of piezoelectric materials with excellent performance has become a current research hotspot. Molecular ferroelectrics have the advantages of adjustable structure, good toughness, and low acoustic impedance, and have great potential in environmental protection processing, low cost, and biocompatibility. Although molecular ferroelectric materials are expected to complement the deficiencies of inorganic ferroelectric materials, their development is relatively lagging behind. The molecular ferroelectrics of single-component organic-inorganic perovskites in the TMCM- _CdCl3 class reported by us in 2017 have higher _d values than barium titanate, but still much lower than other inorganic ferroelectric solid solutions. Therefore, it is crucial to design molecular ferroelectric materials with piezoelectric properties comparable to those of ceramic solid solutions.

Contents of the invention

Purpose of the invention: The purpose of the present invention is to provide a perovskite piezoelectric solid solution material: TMCM-CdBrCl ₂ (TMCM: trimethylchloromethylammonium), which has great application in wearable piezoelectric devices prospect.

Technical solution: the preparation method of a perovskite piezoelectric solid solution according to the present invention, the specific operation steps are as follows:

(1.1), at a temperature of 25°C, add bromomethane and trimethylamine to the acetonitrile solution, and perform ultrasonic dissolution to obtain trimethylchloromethylamine bromide salt solution, which is ready for use;

(1.2), add inorganic matter in the methanol solution that volume fraction is 99.5%, carry out ultrasonic treatment, obtain the methanol suspension of inorganic matter;

(1.3), the obtained trimethylchloromethylamine bromide salt solution is added to the obtained methanol suspension containing inorganic substances, stirred and dissolved to obtain a methanol clear solution containing TMCM- _CdBrCl ;

Evaporate the methanol clear solution containing TMCM- _CdBrCl2 at a temperature of 25°C to obtain TMCM- _CdBrCl2 colorless block crystals;

(1.4), the obtained TMCM-CdBrCl ₂ colorless massive crystals are ball milled to obtain molecular piezoelectric material micropowder;

(1.5), mixing the obtained molecular piezoelectric material micropowder with another methanol solution with a volume fraction of 99.5%, and performing ultrasonic treatment to obtain a methanol clear solution containing molecular piezoelectric material micropowder;

(1.6), drawing 20 μ L of the obtained methanol clarified solution containing the molecular piezoelectric material micropowder, which is spin-coated on a glass substrate coated with ITO to form a film, thereby obtaining TMCM-CdBrCl ₂ Thin film;

(1.7) Perform annealing treatment on the obtained TMCM-CdBrCl ₂ film, and finally obtain a perovskite piezoelectric solid solution, that is, a piezoelectric material film.

Further, in step (1.1), the mass concentration of the trimethylamine is: 30wt% in water;

The molar ratio of bromochloromethane and trimethylamine is 1:1, the volume of the acetonitrile solution is 100ml, and the reaction time for ultrasonic dissolution is 24 hours.

Further, in step (1.2), the inorganic substance is any one of anhydrous cadmium chloride, cadmium chloride monohydrate or cadmium chloride 5/2 hydrate;

The volume of the methanol solution with a volume fraction of 99.5% is 100 ml.

Further, in step (1.3), the volumes of the methanol suspension containing inorganic substances and the trimethylchloromethylamine bromide salt solution used are both 100 ml.

Further, in step (1.4), the time for ball milling is two hours.

Further, in step (1.5), the mass of the molecular piezoelectric material fine powder is 50 mg, and the volume in the methanol solution with a volume fraction of 99.5% is 1 ml.

Further, in step (1.6), the rotational speed of the spin coating is 3000 rpm, and the time is 40 seconds.

Further, the reaction condition of the annealing treatment is: annealing at 120° C. for 30 minutes.

Beneficial effects: Compared with the prior art, the present invention adopts the method to prepare TMCM- _CdBrCl2 perovskite piezoelectric solid solution material and film, and the process at room temperature avoids high-temperature sintering and high-voltage polarization process; its piezoelectric response Excellent (d ₃₃ ＝400–800pC/N), far exceeding the inorganic piezoelectric material BTO (d ₃₃ ＝105pC/N, polarized along the [001] direction), _Tc is as high as 373K; moreover, the molecular material is flexible and can Use chemical strategies such as the fluorination effect to design and control the corresponding physical and chemical properties.

Description of drawings

Fig. 1 is the operation flowchart of the present invention;

Fig. 2 is ferroelectric TMCMCdBrCl in the present invention ₂ warming-cooling reversible DSC comparative schematic diagram;

Fig. 3 is ferroelectric _TMCMCdBrCl among the present invention The comparison schematic diagram of the temperature-variable frequency doubling effect;

Fig. 4 is ferroelectric TMCMCdBrCl in the present invention ε _' under 1MHz the change curve schematic diagram with temperature;

Fig. 5 is a schematic diagram of the TGA spectrum (measurement range 0-850°C) of the ferroelectric TMCMCdBrCl ₂ in the present invention.

Detailed ways

The present invention is further described below in conjunction with the accompanying drawings and specific embodiments; in the following description, many specific details are set forth in order to fully understand the present application, but the present application can be implemented in many other ways different from those described here, Those skilled in the art can make similar improvements without departing from the connotation of the application, so the application is not limited by the specific implementation disclosed below.

A kind of preparation method of perovskite type piezoelectric solid solution of the present invention, its specific operation steps are as follows:

(1.1), at a temperature of 25°C, add bromomethane and trimethylamine to the acetonitrile solution, and perform ultrasonic dissolution to obtain trimethylchloromethylamine bromide salt solution, which is ready for use;

(1.2), add inorganic matter in the methanol solution that volume fraction is 99.5%, carry out ultrasonic treatment, obtain the methanol suspension of inorganic matter;

(1.3), the obtained trimethylchloromethylamine bromide salt solution is added to the obtained methanol suspension containing inorganic substances, stirred and dissolved to obtain a methanol clear solution containing TMCM- _CdBrCl ;

Evaporate the methanol clear solution containing TMCM- _CdBrCl2 at a temperature of 25°C to obtain TMCM- _CdBrCl2 colorless block crystals;

(1.4), the obtained TMCM-CdBrCl ₂ colorless massive crystals are ball milled to obtain molecular piezoelectric material micropowder;

(1.5), mixing the obtained molecular piezoelectric material micropowder with another methanol solution with a volume fraction of 99.5%, and performing ultrasonic treatment to obtain a methanol clear solution containing molecular piezoelectric material micropowder;

(1.6), drawing 20 μ L of the obtained methanol clarified solution containing the molecular piezoelectric material micropowder, which is spin-coated on a glass substrate coated with ITO to form a film, thereby obtaining TMCM-CdBrCl ₂ Thin film;

(1.7) Perform annealing treatment on the obtained TMCM-CdBrCl ₂ film, and finally obtain a perovskite piezoelectric solid solution, that is, a piezoelectric material film.

Further, in step (1.1), the mass concentration of the trimethylamine is: 30wt% in water;

The molar ratio of bromochloromethane and trimethylamine is 1:1, the volume of the acetonitrile solution is 100ml, and the reaction time for ultrasonic dissolution is 24 hours.

Further, in step (1.2), the inorganic substance is any one of anhydrous cadmium chloride, cadmium chloride monohydrate or cadmium chloride 5/2 hydrate;

The volume of the methanol solution with a volume fraction of 99.5% is 100 ml.

Further, in step (1.3), the volumes of the methanol suspension containing inorganic substances and the trimethylchloromethylamine bromide salt solution used are both 100 ml.

Further, in step (1.4), the time for ball milling is two hours.

Further, in step (1.5), the mass of the molecular piezoelectric material fine powder is 50 mg, and the volume in the methanol solution with a volume fraction of 99.5% is 1 ml.

Further, in step (1.6), the rotational speed of the spin coating is 3000 rpm, and the time is 40 seconds.

Further, the reaction condition of the annealing treatment is: annealing at 120° C. for 30 minutes.

The reagents and raw materials used in this example are commercially available common commodities unless otherwise specified.

A method for preparing a perovskite piezoelectric solid solution, the selected piezoelectric material is TMCM-CdBrCl ₂ (Me ₃ NCH ₂ ClCdBrCl ₂ ), the organic-inorganic hybrid perovskite ferroelectric TMCM-CdBrCl ₂ not only has Excellent ferroelectric properties, especially its piezoelectric response;

Specifically, a perovskite-type molecular ferroelectric material, the general formula of the molecular ferroelectric material is ABX ₃ , wherein A is an organic cation (1), B is a metal cation (2), and X is an inorganic anion (3 ), wherein A is an organic cation including: tetramethylamine cation, tetramethylphosphine cation, trimethylchloromethylamine cation, trimethylfluoromethylamine cation, trimethylbromomethylamine cation, trimethylammonium Iodomethylamine cation, trimethyldifluoromethylamine cation, trimethyltrifluoromethylamine cation, trimethylhydroxylamine cation, trimethylethyl cation, trimethylpropyl cation, trimethyl Chloroethyl cation, trimethylamine cation, triethylamine cation, tetraethylamine cation, triethylamine methyl cation, triethylamine chloromethyl cation, triethylamine fluoromethyl cation, triethylamine bromomethyl cation, Triethylamine iodomethyl cation, pyrrolidinium cation, pyrroline cation, quinucidine cation, imidazolium cation, pyridinium cation, aminopyrrolidinium cation, aminoquinucidine cation, piperazine cation or triethylenediamine cation, etc.;

B is a metal cation including: Cd 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 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 thin film preparation process, which provides guidance for the wide-ranging reference of such material thin films.

Example 1:

A method for preparing a perovskite molecular ferroelectric material, the method comprising the following steps:

(1), at a temperature of 25° C., stir and mix chlorobromomethane and trimethylamine in acetonitrile to obtain trimethylchloromethylamine bromide;

(2), in the methanol solution that volume fraction is 99.5%, add inorganic substance cadmium chloride, ultrasonic dissolution obtains inorganic substance solution;

(3), adding the trimethylchloromethylamine bromide salt obtained in the above step (1) into the inorganic solution obtained in the above step (2), stirring and dissolving until clarification;

(4) Slowly evaporate the clear solution obtained in the above step (3) to obtain TMCM-CdBrCl ₂ colorless massive crystals.

A method for preparing a thin film of a perovskite molecular ferroelectric material, the method comprising the following steps:

(1), the molecular ferroelectric material TMCM-CdBrCl ₂ crystal is subjected to ball milling treatment to obtain molecular piezoelectric material micropowder;

(2), the molecular piezoelectric material micropowder obtained in step (1) is dissolved in an organic polar solvent to make it saturated;

(3), above-mentioned solution is dripped on the substrate that has been cleaned, utilizes the spin coating mode to realize the uniform smear of solution, remove solvent in oven;

(4), placing the material described in step (3) on a hot stage for heat annealing treatment, finally obtaining a uniform piezoelectric material film;

(5), the organic polar solution in step (2) comprises: water, methanol, DMF, ethanol, acetone, petroleum ether, ether, chloroform, trichloroethylene, formamide, ethylene glycol, methyl Acetamide, aminoethanol, acetic acid, propanol, butanol, DMSO, acetonitrile, aniline, ethylenediamine, morpholine, pyridine, THF, quinine, toluene and other organic solvents;

The substrate in the step (2) refers to silicon dioxide, quartz, polymeric polymer materials.

Example 2:

A method for preparing a perovskite molecular ferroelectric material, the method comprising the following steps:

(1), at a temperature of 25°C, dichloromethane and trimethylamine were stirred and mixed in acetonitrile to obtain trimethylchloromethylamine chloride salt;

(2), in the methanol solution that volume fraction is 99.5%, add inorganic substance cadmium bromide, ultrasonic dissolution obtains inorganic substance solution;

(3), adding the trimethylchloromethylamine chloride salt obtained in the above step (1) into the inorganic solution obtained in the above step (2), stirring and dissolving until clarification;

(4) Slowly evaporate the clear solution obtained in the above step (3) to obtain TMCM-CdBr ₂ Cl colorless blocky crystals.

A method for preparing a thin film of a perovskite molecular ferroelectric material, the method comprising the following steps:

(1) Perform ball milling on molecular ferroelectric material TMCM-CdBr ₂ Cl crystals to obtain molecular piezoelectric material micropowder;

(2), the molecular piezoelectric material micropowder obtained in step (1) is dissolved in an organic polar solvent to make it saturated;

(3), above-mentioned solution is dripped on the substrate that has been cleaned, utilizes the spin coating mode to realize the uniform smear of solution, remove solvent in oven;

(4), placing the material described in step (3) on a hot stage for heat annealing treatment, finally obtaining a uniform piezoelectric material film;

(5), the organic polar solution in step (2) comprises: water, methanol, DMF, ethanol, acetone, petroleum ether, ether, chloroform, trichloroethylene, formamide, ethylene glycol, methyl Acetamide, aminoethanol, acetic acid, propanol, butanol, DMSO, acetonitrile, aniline, ethylenediamine, morpholine, pyridine, THF, quinine, toluene and other organic solvents;

The substrate in the step (2) refers to silicon dioxide, quartz, polymeric polymer materials.

Example 3:

A method for preparing a perovskite molecular ferroelectric material, the method comprising the following steps:

(1), at a temperature of 25°C, dichloromethane and trimethylamine were stirred and mixed in acetonitrile to obtain trimethylchloromethylamine chloride salt;

(2), in the methanol solution that volume fraction is 99.5%, add inorganic substance manganese bromide, ultrasonic dissolution obtains inorganic substance solution;

(3), adding the trimethylchloromethylamine chloride salt obtained in the above step (1) into the inorganic solution obtained in the above step (2), stirring and dissolving until clarification;

(4) Slowly evaporate the clear solution obtained in the above step (3) to obtain TMCM-MnBr ₂ Cl crystals.

A method for preparing a thin film of a perovskite molecular ferroelectric material, the method comprising the following steps:

(1) The molecular ferroelectric material TMCM-MnBr ₂ Cl crystal is ball milled to obtain molecular piezoelectric material powder;

(2), the molecular piezoelectric material micropowder obtained in step (1) is dissolved in an organic polar solvent to make it saturated;

(3), above-mentioned solution is dripped on the substrate that has been cleaned, utilizes the spin coating mode to realize the uniform smear of solution, remove solvent in oven;

(4), placing the material described in step (3) on a hot stage for heat annealing treatment, finally obtaining a uniform piezoelectric material film;

(5), the organic polar solution in step (2) comprises: water, methanol, DMF, ethanol, acetone, petroleum ether, ether, chloroform, trichloroethylene, formamide, ethylene glycol, methyl Acetamide, aminoethanol, acetic acid, propanol, butanol, DMSO, acetonitrile, aniline, ethylenediamine, morpholine, pyridine, THF, quinine, toluene and other organic solvents;

The substrate in the step (2) refers to silicon dioxide, quartz, polymeric polymer materials.

Example 4:

A method for preparing a perovskite molecular ferroelectric material, the method comprising the following steps:

(1), at a temperature of 25° C., stir and mix chlorobromomethane and trimethylamine in acetonitrile to obtain trimethylchloromethylamine bromide;

(2), in the methanol solution that volume fraction is 99.5%, add inorganic matter manganese chloride, ultrasonic dissolution obtains inorganic matter solution;

(3), adding the trimethylchloromethylamine bromide salt obtained in the above step (1) into the inorganic solution obtained in the above step (2), stirring and dissolving until clarification;

(4) Slowly evaporate the clear solution obtained in the above step (3) to obtain TMCM-MnBrCl ₂ crystals.

A method for preparing a thin film of a perovskite molecular ferroelectric material, the method comprising the following steps:

(1), carry out ball milling treatment to molecular ferroelectric material TMCM-MnBrCl ₂ crystal, obtain molecular piezoelectric material micropowder;

(2), the molecular piezoelectric material micropowder obtained in step (1) is dissolved in an organic polar solvent to make it saturated;

(3), above-mentioned solution is dripped on the substrate that has been cleaned, utilizes the spin coating mode to realize the uniform smear of solution, remove solvent in oven;

(4), placing the material described in step (3) on a hot stage for heat annealing treatment, finally obtaining a uniform piezoelectric material film;

(5), the organic polar solution in step (2) comprises: water, methanol, DMF, ethanol, acetone, petroleum ether, ether, chloroform, trichloroethylene, formamide, ethylene glycol, methyl Acetamide, aminoethanol, acetic acid, propanol, butanol, DMSO, acetonitrile, aniline, ethylenediamine, morpholine, pyridine, THF, quinine, toluene and other organic solvents;

The substrate in the step (2) refers to silicon dioxide, quartz, polymeric polymer materials.

Claims (8)

1. a preparation method of perovskite type piezoelectric solid solution, is characterized in that, concrete operation steps are as follows: (1.1), at a temperature of 25°C, add bromomethane and trimethylamine to the acetonitrile solution, and perform ultrasonic dissolution to obtain trimethylchloromethylamine bromide salt solution, which is ready for use; (1.2), add inorganic matter in the methanol solution that volume fraction is 99.5%, carry out ultrasonic treatment, obtain the methanol suspension of inorganic matter; Wherein, the inorganic substance is any one of anhydrous cadmium chloride, cadmium chloride monohydrate or cadmium chloride 5/2 hydrate; (1.3), the obtained trimethylchloromethylamine bromide salt solution is added to the obtained methanol suspension containing inorganic substances, stirred and dissolved to obtain a methanol clear solution containing TMCM- _CdBrCl ; Evaporate the methanol clear solution containing TMCM- _CdBrCl2 at a temperature of 25°C to obtain TMCM- _CdBrCl2 colorless block crystals; (1.4), the obtained TMCM-CdBrCl ₂ colorless massive crystals are ball milled to obtain molecular piezoelectric material micropowder; (1.5), mixing the obtained molecular piezoelectric material micropowder with another methanol solution with a volume fraction of 99.5%, and performing ultrasonic treatment to obtain a methanol clear solution containing molecular piezoelectric material micropowder; (1.6), drawing 20 μ L of the obtained methanol clarified solution containing the molecular piezoelectric material micropowder, which is spin-coated on a glass substrate coated with ITO to form a film, thereby obtaining TMCM-CdBrCl ₂ Thin film; (1.7), the obtained TMCM-CdBrCl ₂ thin film is annealed to finally obtain a piezoelectric material thin film, that is, a perovskite piezoelectric solid solution. 2. the preparation method of a kind of perovskite type piezoelectric solid solution according to claim 1, is characterized in that, In step (1.1), the trimethylamine is 30wt% trimethylamine aqueous solution in water, The molar ratio of bromochloromethane and trimethylamine is 1:1, the volume of the acetonitrile solution is 100ml, and the reaction time for ultrasonic dissolution is 24 hours. 3. the preparation method of a kind of perovskite type piezoelectric solid solution according to claim 1, is characterized in that, In step (1.2), the volume fraction of the used methanol solution of 99.5% is 100 ml. 4. the preparation method of a kind of perovskite type piezoelectric solid solution according to claim 1 is characterized in that, in step (1.3), used methanol suspension containing inorganic matter and trimethylchloromethylamine The volume of bromine salt solution is 100ml. 5. the preparation method of a kind of perovskite type piezoelectric solid solution according to claim 1, is characterized in that, In step (1.4), the time for the ball milling treatment is two hours. 6. the preparation method of a kind of perovskite type piezoelectric solid solution according to claim 1, is characterized in that, In step (1.5), the mass of the molecular piezoelectric material fine powder is 50 mg, and the volume of the methanol solution with a volume fraction of 99.5% is 1 ml. 7. the preparation method of a kind of perovskite type piezoelectric solid solution according to claim 1, is characterized in that, In step (1.6), the rotational speed of the spin coating is 3000 rpm, and the time is 40 seconds. 8. the preparation method of a kind of perovskite type piezoelectric solid solution according to claim 1, is characterized in that, The reaction condition of the annealing treatment is: annealing at 120° C. for 30 minutes.