CN113594356A

CN113594356A - Ferroelectric oxide and MAxFA1-xPbI30-3 composite film material

Info

Publication number: CN113594356A
Application number: CN202010366737.0A
Authority: CN
Inventors: 吕兴杰; 赵泽恩; 袁国亮
Original assignee: Nanjing University of Science and Technology
Current assignee: Nanjing University of Science and Technology
Priority date: 2020-04-30
Filing date: 2020-04-30
Publication date: 2021-11-02

Abstract

The invention provides a composite thin film material of a ferroelectric oxide and MA _x FA _1- _x PbI ₃ 0-3. The 0-dimensional ferroelectric material with an average particle size of 12-18 nm is used to make the 0-dimensional ferroelectric material uniform. Distributed in the 3-dimensional connected framework formed by MA _x FA _1-x PbI ₃ to obtain the thin film material. Compared with the existing halogen perovskite films, the composite film of ferroelectric oxide and MA _x FA _1‑x PbI ₃ 0‑3 has a large number of nano-ferroelectric domains inside, which can effectively reduce the recombination of photogenerated electron-hole pairs , improving the photovoltaic performance of the material, forming a new class of MA _x FA _1‑x PbI ₃ ferroelectric semiconductor materials.

Description

Ferroelectric oxide and MAxFA1-xPbI30-3 composite film material

Technical Field

The invention relates to MA_xFA_1-xPbI₃A film, especially a ferroelectric adjustable MA_xFA_1-xPbI₃A film and a preparation method thereof belong to the technical field of perovskite.

Background

The 0-dimensional ferroelectric material has the characteristics of wide absorption range and high absorption coefficient, so that the 0-dimensional ferroelectric material can be used as a good light absorber. Thus for MA_xFA_1-xPbI₃The (MA: methyl ammonium, FA: formamidine) thin film material is doped with 0-dimensional ferroelectric materialFurther increasing the light absorption range of the material and generating a built-in electric field to reduce the recombination of electron-hole pairs. Therefore, MA is_xFA_1-xPbI₃The film is combined with 0-dimensional ferroelectric material to form a brand new MA_xFA_1-xPbI₃Ferroelectric semiconductor material, which will improve the existing MA_xFA_1-xPbI₃A simple and easy method for making film ferroelectric.

The 0-3 composite material represents a composite system formed by uniformly distributing nano ferroelectrics (0 dimension) in 3-dimension communicated polymers. The 0-3 composite material is favored by the advantages of easy molding and processing (only the nano ferroelectric powder and the film are mixed together, and the finished product can be obtained by a polymer processing method), good flexibility, easy preparation of a large-area sensor, good comprehensive performance and the like. In the prior art, there are references to increasing MAPbI by composite ferroelectric materials₃The properties of the film. The effect of improving the ferroelectric property is achieved by using a ferroelectric material as a main body, the compounding mode is basically 3-3 compounding, the 0-3 compounding mode is not involved, the changes of the structure and the property of the film due to the addition of the 0-dimensional nano material and the MAPbI caused by the changes are not researched₃Important improvements in thin film photovoltaic performance.

The relevant articles mainly include:

1.Xu,Haowen.Morphology control of organic halide perovskites by adding BiFeO₃nanostructures for efficient solar cell.Scientific reports[J]2019,9,1-8, et al, in MAPbI₃In the spinning and coating process of the precursor solution, BiFeO is added₃The nano structure is added into a precursor solvent to obtain BiFeO₃-MAPbI₃A composite film. BiFeO₃-MAPbI₃Film vs MAPbI₃The absorption strength of the film is increased, the carrier mobility and the diffusion length are increased, and the photovoltaic current is enhanced.

In this article due to BiFeO₃Occupying the bulk of the film material and thus causing large grains in the grown film.

2. The invention discloses a ferroelectric enhanced solar cell and a preparation method thereof (patent application No. CN 209698251A). The invention discloses a ferroelectric enhanced solar cell and a preparation method thereof.A ferroelectric nano material with good crystallinity, such as nano particles, is used for replacing a common film, so that a functional layer has higher remanent polarization strength and cannot influence the transmission of current carriers, and an inorganic ferroelectric material treated by a specific artificial polarization process can also effectively promote the separation and the transmission of the current carriers.

The patent prepares a ferroelectric enhanced solar cell by a method of replacing a thin film by large ferroelectric particles, wherein the large-sized particles are combined in a 3-3 composite mode, and the advantage of flexibility of the thin film material is lost.

In view of the foregoing, many inconsistencies and difficulties are always encountered in designing and preparing composite materials. The more prominent problems are that: it is difficult to produce large-area ferroelectric thin films with good comprehensive properties. At present, the ferroelectric composite material with the best electrical combination property is generally prepared by a hot pressing or sputtering process, and the area of a ferroelectric film prepared by the hot pressing or sputtering method is limited, so that the ferroelectric composite material is not suitable for simple preparation of the composite ferroelectric material. And the main matrix MAPbI of the 0-3 ferroelectric composite material compounded with the nano ferroelectric₃The film-forming property of the film is poor, and the film is not suitable for preparing large-area thin film devices. Therefore, it is still difficult to obtain a large-area ferroelectric thin film having excellent overall properties.

Disclosure of Invention

In order to solve the above problems, the present invention provides a ferroelectric oxide and MA_xFA_1-xPbI₃0-3 composite film material and a preparation method thereof.

The technical solution for realizing the purpose of the invention is as follows: ferroelectric oxide and MA_xFA_1-xPbI₃0-3 composite film material, 0-dimensional ferroelectric material with average particle diameter of about 15nm is uniformly distributed in MA_xFA_1-xPbI₃And obtaining the 0-3 composite film material in the formed 3-dimensional communicated framework.

Preferably, the 0-dimensional ferroelectric material is BaTiO₃、Bi₂FeCrO₆、BiMnO₃、BiCrO₃、YMnO₃Or HoMnO₃Any one of them.

The above ferroelectric oxide and MA_xFA_1-xPbI₃A process for preparing 0-3 composite film material by preparing MA_xFA_1-xPbI₃(x is more than or equal to 0.2 and less than or equal to 0.5) adding 4-6 mu L of 0-dimensional ferroelectric material toluene saturated solution in the process of film, and specifically comprising the following steps:

(1) preparing a 0-dimensional ferroelectric material by a hydrothermal method, and dissolving the 0-dimensional ferroelectric material in toluene to prepare a saturated solution to obtain a precursor solution B;

(2) weighing FAI, MAI and PbI according to the molar ratio of the film material₂Dissolving in gamma-butyrolactone (GBL) to obtain a saturated precursor solution A;

(3) and (3) spin-coating 20-40 mu L of precursor solution A on an ITO glass substrate for 15 seconds at a speed of 900 rpm and 25 seconds at a speed of 4000 rpm, dripping 4-6 mu L of precursor solution B on the surface of the substrate before the second spin-coating, standing for 15 seconds, and finally annealing at 90 ℃ for 10 minutes to remove the organic solvent.

Preferably, the 0-dimensional ferroelectric material is prepared by a hydrothermal method, the reaction process is divided into two sections of temperature rise, firstly, the temperature rise speed is 2 ℃/min, the temperature is raised from room temperature to 200 ℃, the temperature is kept for 3 hours, then, the temperature rise speed is 2 ℃/min, the temperature is raised to a fixed temperature, and the temperature is kept for 2 hours.

Preferably, before spin coating, the ITO glass substrate with the ozone-treated surface is adhered to a spin coater and preheated at 70 ℃ for 5 minutes.

Specifically, the surface ozonization process comprises the following steps: adjusting the air flow rate to 600mL/min, stabilizing the voltage at 180V, placing the substrate in a reaction bottle, controlling the reaction temperature to be 25 ℃, and treating for 30 minutes.

Preferably, the annealing is performed in a high purity nitrogen atmosphere having a purity greater than 99.999%.

Preferably, the annealing is initiated at 60 ℃ and the temperature is raised to 90 ℃ at a heating rate of 2 ℃/min.

Compared with the prior art, the invention has the beneficial effects that:

(1)the method is simple and efficient, and avoids the large particle doping method from carrying out MA treatment_xFA_1-xPbI₃(x is more than or equal to 0.2 and less than or equal to 0.5) the defect concentration is increased and the mobility is reduced caused by the film.

(2) The invention is a film with adjustable ferroelectricity, the adopted material has simple preparation process, easy operation, sufficient raw material source, low production cost, high yield and good repeatability; is not easy to dissolve in common solvent, the thermal decomposition temperature point is relatively high, and the crystal particles are uniform.

Drawings

FIG. 1 is a flow chart of the steps of the present invention.

Figure 2 is an XRD pattern of example 1 of the invention.

FIG. 3 is a P-E spectrum at 1kHz for example 1 of the present invention.

FIG. 4 is a dark current-voltage spectrum of example 1 of the present invention.

FIG. 5 is a plot of remanent polarization at 1kHz for all examples of the invention.

Fig. 6 is a hole mobility map calculated by the SCLC method for all examples of the present invention.

Detailed Description

In order to better illustrate the present invention and facilitate the understanding of the technical solutions of the present invention, the present invention is further described in detail with reference to the following examples. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.

With reference to FIG. 1, the ferroelectric oxide and MA described above_xFA_1-xPbI₃The 0-dimensional ferroelectric material with the average grain diameter of about 15nm is uniformly distributed in the MA by the preparation method of the 0-3 composite film material_xFA_1-xPbI₃The ferroelectric property regulation and control of the film material is realized in the formed 3-dimensional communicated framework, and the method comprises the following steps:

step 1, weighing the 0-dimensional ferroelectric material (BaTiO) according to stoichiometric ratio₃、Bi₂FeCrO₆、BiMnO₃、BiCrO₃、YMnO₃Or HoMnO₃) Adding NaOH solution with concentration of 5mol/L dropwise into corresponding nitrate raw material under magnetic stirring condition until solute is just completely dissolved to form saturated solution, and keeping stirring for 30 minutes. Then adding a certain amount of HNO with the concentration of 3mol/L into the solution₃And (3) stabilizing the pH value of the solution at a fixed value.

And 2, pouring the solution into a PTFE (polytetrafluoroethylene) lining, sealing the reaction kettle and moving the reaction kettle into an oven. The reaction process is divided into two sections of temperature rise, firstly, the temperature rises from room temperature to 200 ℃ at the temperature rise speed of 2 ℃/min, the temperature is kept for 3 hours, then, the temperature rises to a fixed temperature at the temperature rise speed of 2 ℃/min, the temperature is kept for 2 hours, and then, the reaction is naturally cooled to the room temperature.

And 3, taking out the product from the PTFE lining, putting the product into a high-speed centrifuge, adding a proper amount of absolute ethyl alcohol for centrifugal washing, then alternately cleaning the product for 3 times by using deionized water and the absolute ethyl alcohol, putting the precipitate into a drying box at 60 ℃ for heat preservation for 6 hours to obtain a 0-dimensional ferroelectric material, dissolving the 0-dimensional ferroelectric material in a toluene solution to prepare a saturated solution, and obtaining a precursor solution B.

Step 4, weighing FAI, MAI and PbI according to molar ratio₂And dissolved in gamma-butyrolactone (GBL) and dissolved by magnetic stirring at 65 ℃ to prepare a saturated precursor solution A.

And 5, adhering the ITO glass substrate subjected to surface ozone treatment on a spin coater, preheating for 5 minutes at 70 ℃, and spin-coating 20-40 mu L of precursor solution A on the substrate under the conditions of spin-coating for 15 seconds at the speed of 900 rpm and spin-coating for 25 seconds at the speed of 4000 rpm. And dripping 4-6 mu L of precursor solution B on the surface of the substrate in the gap between two spin coating processes, namely after the first spin coating and before the second spin coating, and standing for 15 seconds. And finally, annealing for 10 minutes at 90 ℃ to remove the organic solvent, wherein the annealing atmosphere is high-purity nitrogen with the purity of more than 99.999 percent. The initial temperature of annealing is 60 ℃, the temperature is raised to 90 ℃ at the heating rate of 2 ℃/min, and the MA with adjustable ferroelectricity is obtained_xFA_1-xPbI₃A film.

Example 1

Ferroelectric oxide and MA_xFA_1-xPbI₃0-3 composite filmThe molecular formula of the film is MA_0.2FA_0.8PbI₃X is 0.2, and the added 0-dimensional ferroelectric material is BaTiO₃The method comprises the following steps:

step 1, weighing Ba (NO) according to the stoichiometric ratio of 1:1₃)₂And TiCl₄A NaOH solution with a concentration of 5mol/L was added dropwise with magnetic stirring until the solute was just completely dissolved to form a saturated solution, and stirring was maintained for 30 minutes. Then adding a certain amount of HNO with the concentration of 3mol/L into the solution₃The pH value of the solution is stabilized at 10.5.

And 2, pouring the solution into a PTFE (polytetrafluoroethylene) lining, sealing the reaction kettle and moving the reaction kettle into an oven. The reaction process is divided into two sections of temperature rise, firstly, the temperature rises from room temperature to 200 ℃ at the temperature rise speed of 2 ℃/min, the temperature is preserved for 3 hours, then, the temperature rises to 220 ℃ at the temperature rise speed of 2 ℃/min, the temperature is preserved for 2 hours, and then, the reaction is naturally cooled to the room temperature.

Step 3, taking out the product from the PTFE lining, putting the product into a high-speed centrifuge, adding a proper amount of absolute ethyl alcohol for centrifugal washing, then alternately cleaning the product for 3 times by using deionized water and absolute ethyl alcohol, putting the precipitate into a drying oven at 60 ℃ and preserving the heat for 6 hours to obtain a 0-dimensional ferroelectric material BaTiO₃。

Step 4, weighing FAI, MAI and PbI according to the molar ratio of 0.2:0.8:1₂Dissolving in gamma-butyrolactone (GBL), and magnetically stirring at 65 deg.C to obtain saturated precursor solution A; adding 0-dimensional ferroelectric material BaTiO₃Dissolving in toluene solution to prepare saturated solution and obtain precursor solution B.

And 5, adhering the ITO glass substrate with the surface treated by ozone on a spin coater, preheating for 5 minutes at 70 ℃, and spin-coating 20 mu L of precursor solution A on the substrate under the conditions of spin-coating for 15 seconds at the speed of 900 rpm and spin-coating for 25 seconds at the speed of 4000 rpm. Wherein 4 mul of precursor solution B is dripped on the surface of the substrate in the gap between two spin coating processes and is kept still for 15 seconds. And finally, annealing for 10 minutes at 90 ℃ to remove the organic solvent, wherein the annealing atmosphere is high-purity nitrogen with the purity of more than 99.999 percent. The initial temperature of annealing is 60 ℃, the temperature is raised to 90 ℃ at the heating rate of 2 ℃/min, and the product is obtainedObtain ferroelectric adjustable MA_0.2FA_0.8PbI₃A film. The XRD diffraction pattern of the sample is shown in fig. 2.

The ferroelectric properties of the film of example 1 were studied, using the following specific steps: a proper amount of sample of the composite film is selected, the sample is processed into an original sample to be measured with the thickness of 0.6mm on a tablet press, and conductive silver adhesive is coated on the upper side and the lower side of the tablet press. The test was then performed separately on a Precision Premier II ferroelectric tester. Our investigations of the resulting film found that: the relation curve of the polarization strength P of the composite film and the externally applied electric field strength E shows that the composite film has obvious ferroelectric effect, and the measured ferroelectric hysteresis loop of the film material is shown in figure 3.

Au electrodes with the thickness of 100nm are respectively evaporated on two sides of the film, the hole mobility of the film is tested by an SCLC method, and the obtained dark current-voltage curve is shown in figure 4.

Example 2

This example is a ferroelectric oxide and MA_xFA_1-xPbI₃The 0-3 composite film material and the preparation method thereof are the same as the example 1, except that: in this embodiment, FAI, MAI, and PbI used for preparing the precursor solution a in step 4₂Is 0.5:0.5: 1.

The conditions of the important parameters involved in this example are shown in Table 1, including MA_xFA_1-xPbI₃The film x value, the spin coating amount of the precursor solution A, the type of the 0-dimensional ferroelectric material and the spin coating amount of the precursor solution B.

Example 3

This example is a ferroelectric oxide and MA_xFA_1-xPbI₃The 0-3 composite film material and the preparation method thereof are the same as the example 1, except that: the amount of the precursor solution A spin-coated in step 5 in this example was 40. mu.L.

Example 4

This example is a ferroelectric oxide and MA_xFA_1-xPbI₃The 0-3 composite film material and the preparation method thereof are the same as the example 1, except that: in this embodiment, FAI, MAI, and PbI used for preparing the precursor solution a in step 4₂The molar ratio of (1) to (2) is 0.5:0.5:1, and the amount of spin coating of the precursor solution A in the step 5 is 40. mu.L.

Example 5

This example is a ferroelectric oxide and MA_xFA_1-xPbI₃The 0-3 composite film material and the preparation method thereof are the same as the example 1, except that: the spin coating amount of the precursor solution B in step 5 in this example was 6. mu.l.

Example 6

This example is a ferroelectric oxide and MA_xFA_1-xPbI₃The 0-3 composite film material and the preparation method thereof are the same as the example 1, except that: in this embodiment, FAI, MAI, and PbI used for preparing the precursor solution a in step 4₂The molar ratio of (3) was 0.5:0.5:1, and the amount of spin coating of the precursor solution B in step 5 was 6. mu.l.

Example 7

This example is a ferroelectric oxide and MA_xFA_1-xPbI₃The 0-3 composite film material and the preparation method thereof are the same as the example 1, except that: in this example, the precursor solution A is spin-coated in step 5The amount was 40. mu.L, and the spin-coating amount of the precursor solution B was 6. mu.L.

Example 8

This example is a ferroelectric oxide and MA_xFA_1-xPbI₃The 0-3 composite film material and the preparation method thereof are the same as the example 1, except that: in this embodiment, FAI, MAI, and PbI used for preparing the precursor solution a in step 4₂The molar ratio of (1) to (2) is 0.5:0.5:1, the spin coating amount of the precursor solution A in the step 5 is 40 mul, and the spin coating amount of the precursor solution B is 6 mul.

Example 9

This example is a ferroelectric oxide and MA_xFA_1-xPbI₃The 0-3 composite film material and the preparation method thereof are the same as the example 1, except that: in this example, Bi (NO) was weighed in a stoichiometric ratio of 2:1:1 in step 1₃)₃、Fe(NO₃)₂And Cr (NO)₃)₃。

Example 10

This example is a ferroelectric oxide and MA_xFA_1-xPbI₃The 0-3 composite film material and the preparation method thereof are the same as the example 1, except that: in this example, Bi (NO) is stoichiometrically referred to in step 1₃)₃、Fe(NO₃)₂And Cr (NO)₃)₃FAI, MAI and MAI for preparing the precursor solution A in the step 4PbI₂Is 0.5:0.5: 1.

Example 11

This example is a ferroelectric oxide and MA_xFA_1-xPbI₃The 0-3 composite film material and the preparation method thereof are the same as the example 1, except that: in this example, step 1 is to weigh Bi (NO) in a stoichiometric ratio₃)₃、Fe(NO₃)₂And Cr (NO)₃)₃And the spin coating amount of the precursor solution A in the step 5 is 40 mu L.

Example 12

This example is a ferroelectric oxide and MA_xFA_1-xPbI₃The 0-3 composite film material and the preparation method thereof are the same as the example 1, except that: in this example, step 1 is to weigh Bi (NO) in a stoichiometric ratio₃)₃、Fe(NO₃)₂And Cr (NO)₃)₃FAI, MAI and PbI used for preparing the precursor solution A in the step 4₂The molar ratio of (1) to (2) is 0.5:0.5:1, and the amount of spin coating of the precursor solution A in the step 5 is 40. mu.L.

Example 13

This example is a ferroelectric oxide and MA_xFA_1-xPbI₃The 0-3 composite film material and the preparation method thereof are the same as the example 1, except that: in this example, step 1 is to weigh Bi (NO) in a stoichiometric ratio₃)₃、Fe(NO₃)₂And Cr (NO)₃)₃And the spin coating amount of the precursor solution B in the step 5 is 6 mul.

Example 14

This example is a ferroelectric oxide and MA_xFA_1-xPbI₃The 0-3 composite film material and the preparation method thereof are the same as the example 1, except that: in this example, step 1 is to weigh Bi (NO) in a stoichiometric ratio₃)₃、Fe(NO₃)₂And Cr (NO)₃)₃FAI, MAI and PbI used for preparing the precursor solution A in the step 4₂The molar ratio of (3) was 0.5:0.5:1, and the amount of spin coating of the precursor solution B in step 5 was 6. mu.l.

Example 15

This example is a ferroelectric oxide and MA_xFA_1-xPbI₃The 0-3 composite film material and the preparation method thereof are the same as the example 1, except that: in this example, step 1 is to weigh Bi (NO) in a stoichiometric ratio₃)₃、Fe(NO₃)₂And Cr (NO)₃)₃In the step 5, the spin coating amount of the precursor solution A is 40 mul, and the spin coating amount of the precursor solution B is 6 mul.

Example 16

This example is a ferroelectric oxide and MA_xFA_1-xPbI₃0-3 composite film material and preparation method and implementation thereofExample 1 the same, except that: in this example, step 1 is to weigh Bi (NO) in a stoichiometric ratio₃)₃、Fe(NO₃)₂And Cr (NO)₃)₃FAI, MAI and PbI used for preparing the precursor solution A in the step 4₂The molar ratio of (1) to (2) is 0.5:0.5:1, the spin coating amount of the precursor solution A in the step 5 is 40 mul, and the spin coating amount of the precursor solution B is 6 mul.

Example 17

This example is a ferroelectric oxide and MA_xFA_1-xPbI₃The 0-3 composite film material and the preparation method thereof are the same as the example 1, except that: in this example, Bi (NO) is stoichiometrically referred to in step 1₃)₃And Mn (NO)₃)₂。

Example 18

This example is a ferroelectric oxide and MA_xFA_1-xPbI₃The 0-3 composite film material and the preparation method thereof are the same as the example 1, except that: in this example, Bi (NO) is stoichiometrically referred to in step 1₃)₃And Mn (NO)₃)₂FAI, MAI and PbI used for preparing the precursor solution A in the step 4₂Is 0.5:0.5: 1.

Example 19

This example is a ferroelectric oxide and MA_xFA_1-xPbI₃0-3 timesThe resultant film material and its preparation were the same as in example 1, except that: in this example, Bi (NO) was weighed in a stoichiometric ratio of 1:1 in step 1₃)₃And Mn (NO)₃)₂And the spin coating amount of the precursor solution A in the step 5 is 40 mu L.

Example 20

This example is a ferroelectric oxide and MA_xFA_1-xPbI₃The 0-3 composite film material and the preparation method thereof are the same as the example 1, except that: in this example, step 1 is to weigh Bi (NO) in a stoichiometric ratio₃)₃And Mn (NO)₃)₂FAI, MAI and PbI used for preparing the precursor solution A in the step 4₂The molar ratio of (1) to (2) is 0.5:0.5:1, and the amount of spin coating of the precursor solution A in the step 5 is 40. mu.L.

Example 21

This example is a ferroelectric oxide and MA_xFA_1-xPbI₃The 0-3 composite film material and the preparation method thereof are the same as the example 1, except that: in this example, step 1 is to weigh Bi (NO) in a stoichiometric ratio₃)₃And Mn (NO)₃)₂And the spin coating amount of the precursor solution B in the step 5 is 6 mul.

Example 22

This example is a ferroelectric oxide and MA_xFA_1-xPbI₃0-3 composite film material and its preparationThe preparation process is the same as in example 1, except that: in this example, step 1 is to weigh Bi (NO) in a stoichiometric ratio₃)₃And Mn (NO)₃)₂FAI, MAI and PbI used for preparing the precursor solution A in the step 4₂The molar ratio of (3) was 0.5:0.5:1, and the amount of spin coating of the precursor solution B in step 5 was 6. mu.l.

Example 23

This example is a ferroelectric oxide and MA_xFA_1-xPbI₃The 0-3 composite film material and the preparation method thereof are the same as the example 1, except that: in this example, step 1 is to weigh Bi (NO) in a stoichiometric ratio₃)₃And Mn (NO)₃)₂In the step 5, the spin coating amount of the precursor solution A is 40 mul, and the spin coating amount of the precursor solution B is 6 mul.

Example 24

This example is a ferroelectric oxide and MA_xFA_1-xPbI₃The 0-3 composite film material and the preparation method thereof are the same as the example 1, except that: in this example, step 1 is to weigh Bi (NO) in a stoichiometric ratio₃)₃And Mn (NO)₃)₂FAI, MAI and PbI used for preparing the precursor solution A in the step 4₂The molar ratio of (1) to (2) is 0.5:0.5:1, the spin coating amount of the precursor solution A in the step 5 is 40 mul, and the spin coating amount of the precursor solution B is 6 mul.

Example 25

This example is a ferroelectric oxide and MA_xFA_1-xPbI₃The 0-3 composite film material and the preparation method thereof are the same as the example 1, except that: in this example, Bi (NO) was weighed in a stoichiometric ratio of 1:1 in step 1₃)₃And Cr (NO)₃)₃。

Example 26

This example is a ferroelectric oxide and MA_xFA_1-xPbI₃The 0-3 composite film material and the preparation method thereof are the same as the example 1, except that: in this example, Bi (NO) is stoichiometrically referred to in step 1₃)₃And Cr (NO)₃)₃FAI, MAI and PbI used for preparing the precursor solution A in the step 4₂Is 0.5:0.5: 1.

Example 27

This example is a ferroelectric oxide and MA_xFA_1-xPbI₃The 0-3 composite film material and the preparation method thereof are the same as the example 1, except that: in this example, step 1 is to weigh Bi (NO) in a stoichiometric ratio₃)₃And Cr (NO)₃)₃And the spin coating amount of the precursor solution A in the step 5 is 40 mu L.

Example 28

This example is a ferroelectric oxide and MA_xFA_1-xPbI₃0-3 timesThe resultant film material and its preparation were the same as in example 1, except that: in this example, step 1 is to weigh Bi (NO) in a stoichiometric ratio₃)₃And Cr (NO)₃)₃FAI, MAI and PbI used for preparing the precursor solution A in the step 4₂The molar ratio of (1) to (2) is 0.5:0.5:1, and the amount of spin coating of the precursor solution A in the step 5 is 40. mu.L.

Example 29

This example is a ferroelectric oxide and MA_xFA_1-xPbI₃The 0-3 composite film material and the preparation method thereof are the same as the example 1, except that: in this example, step 1 is to weigh Bi (NO) in a stoichiometric ratio₃)₃And Cr (NO)₃)₃And the spin coating amount of the precursor solution B in the step 5 is 6 mul.

Example 30

This example is a ferroelectric oxide and MA_xFA_1-xPbI₃The 0-3 composite film material and the preparation method thereof are the same as the example 1, except that: in this example, step 1 is to weigh Bi (NO) in a stoichiometric ratio₃)₃And Cr (NO)₃)₃FAI, MAI and PbI used for preparing the precursor solution A in the step 4₂The molar ratio of (3) was 0.5:0.5:1, and the amount of spin coating of the precursor solution B in step 5 was 6. mu.l.

Example 31

This example is an ironElectrooxidation and MA_xFA_1-xPbI₃The 0-3 composite film material and the preparation method thereof are the same as the example 1, except that: in this example, step 1 is to weigh Bi (NO) in a stoichiometric ratio₃)₃And Cr (NO)₃)₃In the step 5, the spin coating amount of the precursor solution A is 40 mul, and the spin coating amount of the precursor solution B is 6 mul.

Example 32

This example is a ferroelectric oxide and MA_xFA_1-xPbI₃The 0-3 composite film material and the preparation method thereof are the same as the example 1, except that: in this example, step 1 is to weigh Bi (NO) in a stoichiometric ratio₃)₃And Cr (NO)₃)₃FAI, MAI and PbI used for preparing the precursor solution A in the step 4₂The molar ratio of (1) to (2) is 0.5:0.5:1, the spin coating amount of the precursor solution A in the step 5 is 40 mul, and the spin coating amount of the precursor solution B is 6 mul.

Example 33

This example is a ferroelectric oxide and MA_xFA_1-xPbI₃The 0-3 composite film material and the preparation method thereof are the same as the example 1, except that: in this example, Y (NO) is stoichiometrically used in step 1₃)₃And Mn (NO)₃)₂。

Example 34

This example is a ferroelectricOxide and MA_xFA_1-xPbI₃The 0-3 composite film material and the preparation method thereof are the same as the example 1, except that: in this example, in step 1, Y (NO) was weighed in a stoichiometric ratio of 1:1₃)₃And Mn (NO)₃)₂FAI, MAI and PbI used for preparing the precursor solution A in the step 4₂Is 0.5:0.5: 1.

Example 35

This example is a ferroelectric oxide and MA_xFA_1-xPbI₃The 0-3 composite film material and the preparation method thereof are the same as the example 1, except that: in this example, step 1 is called Y (NO) in stoichiometric ratio₃)₃And Mn (NO)₃)₂And the spin coating amount of the precursor solution A in the step 5 is 40 mu L.

Example 36

This example is a ferroelectric oxide and MA_xFA_1-xPbI₃The 0-3 composite film material and the preparation method thereof are the same as the example 1, except that: in this example, step 1 is called Y (NO) in stoichiometric ratio₃)₃And Mn (NO)₃)₂FAI, MAI and PbI used for preparing the precursor solution A in the step 4₂The molar ratio of (1) to (2) is 0.5:0.5:1, and the amount of spin coating of the precursor solution A in the step 5 is 40. mu.L.

Example 37

This example is a ferroelectric oxide and MA_xFA_1-xPbI₃The 0-3 composite film material and the preparation method thereof are the same as the example 1, except that: in this example, step 1 is called Y (NO) in stoichiometric ratio₃)₃And Mn (NO)₃)₂And the spin coating amount of the precursor solution B in the step 5 is 6 mul.

Example 38

This example is a ferroelectric oxide and MA_xFA_1-xPbI₃The 0-3 composite film material and the preparation method thereof are the same as the example 1, except that: in this example, step 1 is called Y (NO) in stoichiometric ratio₃)₃And Mn (NO)₃)₂FAI, MAI and PbI used for preparing the precursor solution A in the step 4₂The molar ratio of (3) was 0.5:0.5:1, and the amount of spin coating of the precursor solution B in step 5 was 6. mu.l.

Example 39

This example is a ferroelectric oxide and MA_xFA_1-xPbI₃The 0-3 composite film material and the preparation method thereof are the same as the example 1, except that: in this example, step 1 is called Y (NO) in stoichiometric ratio₃)₃And Mn (NO)₃)₂In the step 5, the spin coating amount of the precursor solution A is 40 mul, and the spin coating amount of the precursor solution B is 6 mul.

Example 40

This example is a ferroelectric oxide and MA_xFA_1-xPbI₃The 0-3 composite film material and the preparation method thereof are the same as the example 1, except that: in this example, step 1 is called Y (NO) in stoichiometric ratio₃)₃And Mn (NO)₃)₂FAI, MAI and PbI used for preparing the precursor solution A in the step 4₂The molar ratio of (1) to (2) is 0.5:0.5:1, the spin coating amount of the precursor solution A in the step 5 is 40 mul, and the spin coating amount of the precursor solution B is 6 mul.

EXAMPLE 41

This example is a ferroelectric oxide and MA_xFA_1-xPbI₃The 0-3 composite film material and the preparation method thereof are the same as the example 1, except that: in step 1 of this example, Ho (NO) was weighed in a stoichiometric ratio of 1:1₃)₃And Mn (NO)₃)₂。

Example 42

This example is a ferroelectric oxide and MA_xFA_1-xPbI₃The 0-3 composite film material and the preparation method thereof are the same as the example 1, except that: in this example, Ho (NO) is used as the stoichiometric ratio in step 1₃)₃And Mn (NO)₃)₂FAI, MAI and PbI used for preparing the precursor solution A in the step 4₂Is 0.5:0.5: 1.

Example 43

This example is a ferroelectric oxide and MA_xFA_1-xPbI₃The 0-3 composite film material and the preparation method thereof are the same as the example 1, except that: in this example, step 1 is stoichiometrically referred to as Ho (NO)₃)₃And Mn (NO)₃)₂And the spin coating amount of the precursor solution A in the step 5 is 40 mu L.

Example 44

This example is a ferroelectric oxide and MA_xFA_1-xPbI₃The 0-3 composite film material and the preparation method thereof are the same as the example 1, except that: in this example, step 1 is stoichiometrically referred to as Ho (NO)₃)₃And Mn (NO)₃)₂FAI, MAI and PbI used for preparing the precursor solution A in the step 4₂The molar ratio of (1) to (2) is 0.5:0.5:1, and the amount of spin coating of the precursor solution A in the step 5 is 40. mu.L.

Example 45

This example is a ferroelectric oxide and MA_xFA_1-xPbI₃The 0-3 composite film material and the preparation method thereof are the same as the example 1, except that: in this example, step 1 is stoichiometrically referred to as Ho (NO)₃)₃And Mn (NO)₃)₂And the spin coating amount of the precursor solution B in the step 5 is 6 mul.

Example 46

This implementationExample A ferroelectric oxide and MA_xFA_1-xPbI₃The 0-3 composite film material and the preparation method thereof are the same as the example 1, except that: in this example, step 1 is stoichiometrically referred to as Ho (NO)₃)₃And Mn (NO)₃)₂FAI, MAI and PbI used for preparing the precursor solution A in the step 4₂The molar ratio of (3) was 0.5:0.5:1, and the amount of spin coating of the precursor solution B in step 5 was 6. mu.l.

Example 47

This example is a ferroelectric oxide and MA_xFA_1-xPbI₃The 0-3 composite film material and the preparation method thereof are the same as the example 1, except that: in this example, step 1 is stoichiometrically referred to as Ho (NO)₃)₃And Mn (NO)₃)₂In the step 5, the spin coating amount of the precursor solution A is 40 mul, and the spin coating amount of the precursor solution B is 6 mul.

Example 48

This example is a ferroelectric oxide and MA_xFA_1-xPbI₃The 0-3 composite film material and the preparation method thereof are the same as the example 1, except that: in this example, step 1 is stoichiometrically referred to as Ho (NO)₃)₃And Mn (NO)₃)₂FAI, MAI and PbI used for preparing the precursor solution A in the step 4₂The molar ratio of (1) to (2) is 0.5:0.5:1, the spin coating amount of the precursor solution A in the step 5 is 40 mul, and the spin coating amount of the precursor solution B is 6 mul.

The conditions of the important parameters involved in this example are shown in Table 1, including MA_xFA_1-xPbI₃Film X value, precursor solution A spin coating amount and 0-dimensional ironThe type of the electric material and the spin coating amount of the precursor solution B.

FIG. 5 is a graph of remanent polarization at 1kHz for examples 1-48 of the present invention. FIG. 6 is a spectrum of hole mobility calculated by SCLC method according to examples 1-48 of the present invention.

Table 1 examples conditions of the respective reactions and parameters

The embodiments of the present invention have been described in detail with reference to the above examples, but the present invention is not limited to the above embodiments, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.

Claims

1. a thin film material of ferroelectric oxide and MA _x FA _1-x PbI ₃ 0-3 composite, it is characterized in that, with the 0-dimensional ferroelectric material of average particle diameter 12～18nm, this 0-dimensional ferroelectric material It is uniformly distributed in the 3-dimensional connected framework formed by MA _x FA _1-x PbI ₃ to obtain the 0-3 composite thin film material.

2 . The thin film material according to claim 1 , wherein the 0-dimensional ferroelectric material is any one of BaTiO ₃ , Bi ₂ FeCrO ₆ , BiMnO ₃ , BiCrO ₃ , YMnO ₃ or HoMnO ₃ . 3 .

3. a preparation method of film material as claimed in claim 1 or 2, is characterized in that, in preparation MA _x FA _1-x PbI ₃ thin film process, 0 dimension ferroelectric material is added in toluene solution to obtain saturated solution, and then take 4-6 μL of saturated solution to obtain the thin film material by spin coating method.

4. method as claimed in claim 3, is characterized in that, comprises the steps:

(1) Prepare a 0-dimensional ferroelectric material by a hydrothermal method, dissolve it in a toluene solution to make a saturated solution, and obtain a precursor solution B;

(2) Weighing FAI, MAI and PbI ₂ according to the molar ratio of the film material, and dissolving them in γ-butyrolactone to obtain a saturated precursor solution A;

(3) On the ITO glass substrate, 20-40 μL of precursor solution A was spin-coated at a speed of 900 rpm for 15 seconds and then at a speed of 4000 rpm for 25 seconds. Before coating, 4-6 μL of precursor solution B was dropped on the surface of the substrate, and kept for 15 seconds, and finally annealed at 90 °C for 10 minutes to remove the organic solvent.

5. method as claimed in claim 4 is characterized in that, adopts hydrothermal method to prepare 0-dimensional ferroelectric material, reaction process is divided into two sections of temperature rise, at first rise to 200 ℃ from room temperature with the heating rate of 2 ℃/min , and kept for 3 hours, then raised to a fixed temperature at a heating rate of 2 °C/min, and kept for 2 hours.

6. The method according to claim 4, characterized in that, before spin coating, the ITO glass substrate with surface ozone treatment is adhered to a spin coater, and then preheated at 70° C. for 5 minutes.

7. The method of claim 4, wherein the annealing is performed in a high-purity nitrogen atmosphere with a purity greater than 99.999%.

8 . The method of claim 4 , wherein the initial temperature of annealing is 60° C., and the temperature is raised to 90° C. at a heating rate of 2° C./min. 9 .