CN113667457B - Ferroelectric material with second harmonic effect and preparation method thereof - Google Patents
Ferroelectric material with second harmonic effect and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of materials, and discloses a ferroelectric material with a second harmonic effect and a preparation method thereof. The structural formula of the ferroelectric material is A m (MX n )(M'Y n' ) Wherein A isAn organic cation, M and M' are each independently a metal cation, X and Y are each independently selected from the group consisting of halide, SCN ‑ 、CN ‑ 、N 3 ‑ 、NO 3 ‑ 、BF 4 ‑ And ClO 4 ‑ M is an integer of 1 to 5, n is an integer of 0 to 10, and n' is an integer of 3 to 11. The ferroelectric material provided by the invention has the advantages of large entropy change and enthalpy, high phase change temperature and stable temperature and easiness in regulation and control. In addition, the invention also provides a method for preparing the ferroelectric material with the second harmonic effect, and the method has the advantages of simple steps and low cost.
Description
Technical Field
The invention relates to the technical field of materials, in particular to a ferroelectric material with a second harmonic effect and a preparation method thereof.
Background
As is well known, people's daily life is closely related to latent heat materials, and latent heat generated by phase change of materials is utilized to realize heat storage so as to realize energy conservation and efficient utilization of energy. Existing solid state refrigeration technologies (compression refrigeration, magnetic refrigeration, electric refrigeration, etc.) have received increasing attention in recent decades. Needless to say, the technologies all require the material to undergo solid-solid phase transition under the driving of external conditions to cause entropy change and temperature change, and the material needs to undergo large entropy change to achieve good refrigeration effect. And the large entropy change material also has rich application prospects, such as monitoring, heat storage and the like. Materials with large entropy changes are rare at present.
Nonlinear optics studies the nonlinear interaction of substances with electric fields under strong light by changing the phase, frequency or amplitude of electromagnetic waves input to a material, and plays a crucial role in modern electronics and photonics. And nonlinear crystals are widely applied, such as all-solid-state lasers, optical communication, advanced instruments and the like. Ultraviolet light generated by optical crystal materials is an indispensable part of more and more short-wave light sources in the application of the fields of semiconductor lithography, precision manufacturing, biological genetic engineering and the like. Second Harmonic Generation (SHG), the most important nonlinear optical phenomenon, has attracted considerable interest from many branches of science and technology. In the field of molecular materials, compounds having the SHG effect are receiving much attention for their potential applications in communication, optical computing, optical data storage, optical information processing, and the like.
Ferroelectric, as an important electroactive substance, can realize spontaneous polarization (Ps) storage and switching. The advent of ferroelectricity has created a variety of photoelectric effects, while the coupling of ferroelectricity with other physical properties has brought about new concepts for electronic and optoelectronic applications. Therefore, ferroelectrics are the most promising high performance capacitor candidates with high energy storage density and fast discharge rate. By deepening the understanding of the structure-performance effect, great efforts have been made to advance the development of ferroelectrics. At present, ferroelectric materials are widely used in the fields of storage, field effect transistors, infrared detection and imaging devices, ultrasonic and surface acoustic wave devices, optoelectronic devices and the like. However, these functional properties are currently limited to their presence in the material alone, which greatly limits their use.
Organic-inorganic hybrid materials are receiving wide attention due to their special structural characteristics and exceptional photoelectric characteristics. Especially, organic-inorganic hybrid crystal materials have made a great breakthrough in photoelectric applications such as solar cell light absorbers, light emitting diodes, photodetectors and the like due to tunable band gaps, high carrier mobility and high extinction coefficients. Moreover, the materials usually have first-order phase change under external stimulation and are accompanied by thermal effect, so that the materials become ideal materials for providing large entropy change. The organic-inorganic hybrid material has rich chemical adjustability and structural diversity, and provides possibility for multiple functionalities of the material, such as large entropy change, large nonlinear effect, ferroelectric property and the like. In addition, the material also has the advantages of environmental protection, high efficiency, energy conservation, high reliability, easy synthesis and the like, so that the material is expected to replace the traditional single-function material.
Therefore, it is necessary to find a ferroelectric material with larger entropy change and enthalpy change, higher phase change and stable temperature and easy regulation.
Disclosure of Invention
The invention aims to overcome the technical problems of small entropy change, poor adjustability and the like in the prior art, and provides a ferroelectric material with a second harmonic effect, which has the advantages of large entropy change and enthalpy, high phase change temperature and stable temperature and easiness in adjustment and control.
In order to achieve the above object, a first aspect of the present invention provides a ferroelectric material having a second harmonic effect, the ferroelectric material having a structural formula of A m (MX n )(M'Y n' ) Wherein A is an organic cation, M and M' are each independently a metal cation, X and Y are each independently selected from the group consisting of halide, SCN - 、CN - 、N 3 - 、NO 3 - 、BF 4 - And ClO 4 - M is an integer of 1 to 5, n is an integer of 0 to 10, and n' is an integer of 3 to 11.
In a second aspect, the present invention provides a method for preparing a material having a second harmonic effect, the method comprising: contacting an inorganic metal salt with a source of organic cations in the presence of a polar solvent; wherein the anion in the inorganic metal salt is selected from halide ion and SCN - 、CN - 、N 3 - 、NO 3 - 、BF 4 - And ClO 4 - At least one of (1).
Compared with the prior art, the technical scheme provided by the invention at least has the following advantages:
(1) The ferroelectric material with the second harmonic effect is a hybrid material with organic and inorganic components, wherein the structural formula of the material contains organic cations, metal ions, halogen ions and other anion groups, so that the chemical adjustability, functional diversity and structural flexibility are improved; in addition, the ferroelectric material provided by the invention is crystallized in the ferroelectric space group. In a preferred embodiment of the present invention, there is provided a material ((C) having independent square pyramids and triangular pyramids 4 H 10 NS) 2 (SbCl 5 )(SbCl 3 ) Or (C) 4 H 10 NS) 2 (SbBr 5 )(SbBr 3 ) ) such that the material undergoes a significant first-order solid-solid phase transition driven by temperature and is therefore able to exhibit a large entropy and enthalpy change.
(2) The ferroelectric material provided by the invention has first-order solid-state phase transition, and replaces the traditional gas compression technology(ii) a Compared with the traditional phase-change material, the ferroelectric material provided by the invention has high phase-change temperature which can reach 481K; the stability is good, and the stable temperature can reach 520K; entropy change in the phase change process is large and can reach 145J K -1 mol -1 And the enthalpy change value can reach 69563J mol -1 . The ferroelectric material provided by the invention can be used in the fields of energy storage, refrigeration, random access memories, electro-optical display, nonlinear optics and the like.
(3) The invention also provides a method for preparing the ferroelectric material with the second harmonic effect, which has the advantages of simple steps and low cost.
Drawings
FIG. 1 is a schematic structural diagram of a ferroelectric material prepared in example 1 of the present invention at room temperature (293K);
FIG. 2 is a graph showing the heat flow of a ferroelectric material prepared in example 1 of the present invention as a function of temperature;
FIG. 3 is a thermogravimetric plot of a ferroelectric material prepared in example 1 of the present invention;
FIG. 4 is a graph of the room temperature second harmonic signal of the ferroelectric material prepared in example 1 of this invention;
fig. 5 is a hysteresis loop diagram of a ferroelectric material prepared in example 1 of the present invention;
FIG. 6 is a schematic structural diagram of a ferroelectric material prepared in example 2 of the present invention at room temperature (293K);
FIG. 7 is a graph showing the heat flow as a function of temperature for a ferroelectric material prepared in example 2 of the present invention;
FIG. 8 is a thermogravimetric plot of a ferroelectric material prepared in example 2 of the present invention;
FIG. 9 is a graph of room temperature second harmonic signals for ferroelectric material prepared in example 2 of this invention;
fig. 10 is a hysteresis loop diagram of the ferroelectric material prepared in example 2 of the present invention.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In the present invention, the alkyl group having 1 to 4 carbon atoms may be a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group or a tert-butyl group. C1-C6 alkyl is analogous thereto.
The C1-C4 saturated monohydric alcohol can be methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol or tert-butanol.
In order to achieve the above object, a first aspect of the present invention provides a ferroelectric material having a second harmonic effect, the ferroelectric material having a structural formula of A m (MX n )(M'Y n' ) Wherein A is an organic cation, M and M' are each independently a metal cation, X and Y are each independently selected from the group consisting of halide, SCN - 、CN - 、N 3 - 、NO 3 - 、BF 4 - And ClO 4 - M is an integer from 1 to 5 (e.g., any of 1,2, 3,4, or 5), n is an integer from 0 to 10 (e.g., any of 0, 1,2, 3,4, 5, 6, 7, 8, 9, or 10), and n' is an integer from 3 to 11 (e.g., any of 3,4, 5, 6, 7, 8, 9, 10, or 11).
According to some embodiments of the invention, a may be selected from at least one of the following cations of compounds and derivatives thereof: piperidine, thiomorpholine, 1,3-thiazinane, 1,4-azaphosphacyclohexane, 1,3-azaphosphacyclohexane, 1,2,4-thiadioxane, 6-dihydro-1,3-thiazine, 4H-1,4-thiazine, 3,4-dihydro-2H-1,3-thiazine, 2-methylthiomorpholine, 2-thiomorpholine, (2R) -2-methylthiomorpholine or (2S) -2-methylthiomorpholine.
According to some embodiments of the invention, the derivative is derived from one or more carbon atoms on the ring of the compound parent, optionally substituted with: sulfur, nitrogen, phosphorus, oxygen, halogen, C1-C4 alkyl.
According to some embodiments of the invention, the derivative is a compound wherein one or more hydrogen atoms on the compound parent is optionally replaced by an atom or group selected from: halogen, C1-C6 alkyl, hydroxyl, carbonyl or azo.
According to some embodiments of the invention, a is selected from one of the cations of thiomorpholine, 2-methylthiomorpholine, 2-thiomorpholine alcohol, (2R) -2-methylthiomorpholine or (2S) -2-methylthiomorpholine.
According to some embodiments of the invention, M and M' are each independently selected from at least one of the following metal cations: k is + 、Rb + 、Cs + 、Ag + (monovalent metal cation), mn 2+ 、Fe 2+ 、Co 2+ 、Ni 2+ 、Cu 2+ 、Zn 2+ 、Cd 2+ 、Pb 2+ 、In 2+ (divalent metal cation), in 3+ 、Sb 3+ And Bi 3+ (trivalent metal cations);
preferably, M and M' are each independently selected from Sb 3+ And/or Bi 3+ 。
According to some embodiments of the invention, X and Y are each independently selected from F - 、Cl - 、Br - 、I - 、SCN - 、CN - 、N 3 - 、NO 3 - 、BF 4 - And ClO 4 - Preferably selected from Cl - And/or Br - 。
According to some embodiments of the present invention, the ferroelectric material has a phase transition temperature of 100 to 600K, preferably 200 to 500K; the entropy becomes 20-200J K -1 mol -1 Preferably 50-150J K -1 mol -1 (ii) a The enthalpy change is 2000-80000J mol -1 Preferably from 5000 to 70000J mol -1 (ii) a The stable temperature is 400-600K, preferably 450-550K; the ferroelectric polarization value is 0.3-20 μ C cm -2 Preferably 0.4 to 10 μ C cm -2 。
According to some embodiments of the invention, the ferroelectric material is (C) 4 H 10 NS) 2 (SbCl 5 )(SbCl 3 ) Or (C) 4 H 10 NS) 2 (SbBr 5 )(SbBr 3 )。
In a second aspect, the present invention provides a method for preparing a ferroelectric material having a second harmonic effect. The invention adopts a diffusion method (solution diffusion method) to prepare the ferroelectric material. Specifically, a salt solution containing organic cations and an inorganic metal salt solution are mixed, stirred uniformly, sealed and kept stand until crystals are separated out.
According to some embodiments of the invention, the method comprises: contacting an inorganic metal salt with a source of organic cations in the presence of a polar solvent; wherein the anion in the inorganic metal salt is selected from halide ion and SCN - 、CN - 、N 3 - 、NO 3 - 、BF 4 - And ClO 4 - At least one of (1).
In the present invention, the inorganic metal salt may be obtained by dissolving a metal oxide or a metal halide in an acid, wherein the acid is an inorganic acid, and is preferably at least one selected from the group consisting of hydrochloric acid, hydrobromic acid, hydroiodic acid, hydrofluoric acid, nitric acid and perchloric acid.
In the present invention, the organic cation source may be selected from at least one hydrochloride of the following compounds: piperidine, thiomorpholine, 1,3-thiazinane, 1,4-azaphosphacyclohexane, 1,3-azaphosphacyclohexane, 1,2,4-thiadioxane, 6-dihydro-1,3-thiazine, 4H-1,4-thiazine, 3,4-dihydro-2H-1,3-thiazine, 2-methylthiomorpholine, 2-thiomorpholine, (2R) -2-methylthiomorpholine, or (2S) -2-methylthiomorpholine.
According to some embodiments of the invention, the ratio of the total molar amount of metal elements in the inorganic metal salt to the molar amount of the organic cation source is 1: (0.5-10), preferably 1: (1-5).
According to some embodiments of the invention, the polar solvent is selected from at least one of water, a C1-C4 saturated monohydric alcohol, N-dimethylformamide, and acetonitrile; preferably at least one selected from the group consisting of water, methanol, ethanol and N, N-dimethylformamide.
According to some embodiments of the invention, the contacting is by: an inorganic metal salt is added to a solution of an organic cation source.
According to some embodiments of the invention, the solution of the organic cation source is obtained by dissolving the organic cation source in a polar solvent.
Preferably, the concentration of the organic cation in the solution of the organic cation source is 0.5 to 5mol/L.
According to some embodiments of the invention, the organic cation is added at a rate of 0.01 to 0.5mmol/min, preferably 0.05 to 0.2mmol/min, relative to 1mmol of the metal element in the inorganic metal salt.
According to some embodiments of the invention, the temperature of the contacting is 20-120 ℃, preferably 20-80 ℃; the time is 1-5h, preferably 1-3h.
According to some embodiments of the invention, the organic cation source is thiomorpholine hydrochloride.
According to some embodiments of the invention, the inorganic metal salt is SbCl 3 Or SbBr 3 。
According to a preferred embodiment, the method comprises the following steps:
(a) Antimony chloride (SbCl) 3 ) Mixing with hydrochloric acid (e.g., 36wt% to 38wt% hydrochloric acid) to obtain a metal salt solution of Sb; wherein, the adding amount of hydrochloric acid is 3-8mL relative to 1mmol of antimony chloride;
(b) Mixing thiomorpholine hydrochloride with water to obtain a thiomorpholine salt solution; wherein, the adding amount of water is 1-3mL relative to 1mmol of antimony chloride;
(c) Slowly adding a thiomorpholine salt solution into a Sb metal salt solution at the temperature of 20-30 ℃, then stirring, heating the solution to 60-90 ℃ if precipitates exist, continuously stirring until the thiomorpholine salt solution is completely dissolved, sealing and standing for 12-30h, and filtering and storing after crystals are separated out; wherein the rate of addition of the thiomorpholine salt solution is 0.05 to 0.2mmol/min relative to 1mmol of antimony chloride.
In the present invention, the post-treatment of the reaction is not particularly limited as long as the requirements of the present invention can be satisfied, and for example, it can be performed in the following manner: and (3) sealing and standing the reacted system for 1-48h, and after crystals are separated out, carrying out solid-liquid separation (for example, filtration) to obtain a pure product (namely the ferroelectric material of the invention).
The invention also provides a ferroelectric material with second harmonic effect prepared by the method of the second aspect.
The present invention will be described in detail below by way of examples.
In the following examples, the raw materials used were all obtained commercially without specific description.
Example 1
This example is for the purpose of illustrating the ferroelectric material (C) of the present invention 4 H 10 NS) 2 (SbCl 5 )(SbCl 3 ) Preparation of
1mmol of antimony chloride (SbCl) was weighed 3 ) Adding 5mL of hydrochloric acid (37 wt%) into a 50mL beaker to dissolve the Sb until the Sb is completely dissolved to obtain a metal salt solution of Sb; then adding 2mL of water into another 50mL beaker, and adding 2mmol of thiomorpholine hydrochloride into the water to completely dissolve the thiomorpholine hydrochloride in the beaker to obtain a salt solution of the thiomorpholine; then, slowly adding a thiomorpholine salt solution into a first beaker (a Sb-containing metal salt solution) along the wall of the beaker at 25 ℃ for 0.5 h; stirring with glass rod, heating to 80 deg.C, stirring to dissolve completely, sealing, standing for 24 hr, separating out crystal, filtering, and storing to obtain ferroelectric material (C) 4 H 10 NS) 2 (SbCl 5 )(SbCl 3 )。
Compounds were characterized by single crystal X-ray diffraction: crystallizing at room temperature (293K) in polar ferroelectric space group Cmc2 1 Belong to polar point group C 2v (mm 2) cell constant of
Wherein the asymmetric unit comprises an organothiomorpholine cation, an independent SbCl 5 Tetragonal pyramid and SbCl 3 Triangular pyramid, make the structure form a zero-dimensional structure.
Differential calorimetry (DSC) experiment characterizes the phase change of the material, the result shows that the material has an endothermic peak at 444K and an exothermic peak at 359K, and the huge entropy change value obtained by integration is 137J K -1 mol -1 The enthalpy change value accompanied by it is 60814J mol -1 。
The thermogravimetric curve shows that the material can be stabilized to 500K. In addition, the material showed 4 times the second harmonic signal intensity of potassium dihydrogen phosphate (KDP). Ferroelectric test shows that the material shows a ferroelectric hysteresis loop, and the electric polarization value can reach 1.83 mu C cm -2 。
FIG. 1 is a schematic view of the present embodiment at room temperature (293K); the crystals in the figure crystallize in the orthogonal ferroelectric space group at room temperature.
As shown in FIG. 2, the Heat Flow (Heat Flow) of the present embodiment is a graph showing a temperature-dependent change in the temperature rise curve accompanied by an endothermic peak at 444K; the cooling curve is accompanied by an exothermic peak at 359K. The entropy change associated with the ramp-up and ramp-down process by integrating the curves in FIG. 2 is 137J K -1 mol -1 。
As shown in fig. 3, which is a thermogravimetric plot of this example, the result shows that the material can be stabilized to 470K.
As shown in fig. 4, which is a room temperature second harmonic signal diagram of this example, the results show that the material has a second harmonic signal intensity 4 times KDP.
As shown in FIG. 5, which is a hysteresis chart of this example, the result shows that the saturation polarization of the material can reach 1.83 μ C cm -2 。
Example 2
This example is for the purpose of illustrating the ferroelectric material (C) of the present invention 4 H 10 NS) 2 (SbBr 5 )(SbBr 3 ) Preparation of
Weighing 1mmol of antimony bromide (SbBr) 3 ) Adding 5mL of hydrobromic acid (47 wt%) into a 50mL beaker to dissolve the hydrobromic acid completely to obtain a metal salt solution of Sb; then adding 2mL of water into another 50mL beaker, and adding 2mmol of thiomorpholine hydrochloride into the water to completely dissolve the thiomorpholine hydrochloride in the beaker to obtain a salt solution of the thiomorpholine; subsequently, the salt solution of thiomorpholine is brought to 25 ℃Slowly adding the mixture into a first beaker (containing Sb metal salt solution) along the wall of the beaker, and finishing the adding within 0.5 h; stirring with glass rod, heating to 80 deg.C if precipitate exists, stirring to dissolve completely, sealing, standing for 24 hr, filtering to obtain ferroelectric material (C) 4 H 10 NS) 2 (SbBr 5 )(SbBr 3 )。
Compounds were characterized by single crystal X-ray diffraction: crystallizing at room temperature (293K) in polar ferroelectric space group Cmc2 1 This belongs to the polar point group C 2v (mm 2) cell constant of
The asymmetric unit comprises an organothiomorpholine cation, an independent SbBr 5 Tetragonal pyramid and SbBr 3 Triangular pyramid, make the structure form a zero-dimensional structure.
Differential calorimetry (DSC) experiment represents the phase change of the material, the result shows that the material has an endothermic peak at 481K and an exothermic peak at 385K, and the huge entropy change value obtained by integration is 145J K -1 mol -1 The enthalpy change value accompanied is 69563J mol -1 。
The thermogravimetric curve shows that the material can be stabilized to 520K. In addition, the material showed a second harmonic signal intensity 3 times that of KDP. Ferroelectric test shows that the material shows a hysteresis loop and the electric polarization value is 0.44 mu C cm -2 。
FIG. 6 is a schematic view showing the construction of the room temperature (293K) according to the present embodiment; the crystals in the figure crystallize in the orthogonal ferroelectric space group at room temperature.
As shown in FIG. 7, it is a graph of Heat Flow (Heat Flow) with temperature in the present example, which shows an endothermic peak at 481K in the temperature rising curve; the cooling curve is accompanied by an exothermic peak at 385K. The entropy change during the temperature rise and the temperature fall obtained by integrating the curves in the graph is 145J K -1 mol -1 。
As shown in fig. 8, which is a thermogravimetric plot of this example, the result indicates that the material can be stabilized to 490K.
As shown in fig. 9, which is a room temperature second harmonic signal diagram of this example, the results show that the material has a second harmonic signal intensity 3 times KDP.
As shown in FIG. 10, which is a hysteresis chart of this example, the result shows that the saturation polarization of the material can reach 0.44 μ C cm -2 。
Comparative example 1
The procedure is as in example 1, except that the thiomorpholine hydrochloride in example 1 is replaced with thiazolidine hydrochloride to give a one-dimensional perovskite [ (CH) 2 ) 3 NH 2 S] 2 SbCl 5 。
Compounds were characterized by single crystal X-ray diffraction: the results show that the compound crystallizes in the monoclinic space group P2 at room temperature 1 N, unit cell constant of
β＝90.489(1)°，
The asymmetric unit comprises two organic thiazolidine cations and an independent SbCl 5 A square pyramid. The compound does not exhibit second harmonic and ferroelectric properties due to its presence in a centrally symmetric nonpolar space group.
Differential calorimetry (DSC) experiment characterizes the phase change of the material, the result shows that the material has an endothermic peak at 308K and an exothermic peak at 304K, and a small entropy change value of 0.77J K is obtained by integration -1 mol -1 The enthalpy change accompanying this is 236.2J mol -1 。
Comparative example 2
The procedure is as in example 1, except that lead bromide is used in place of antimony chloride in example 1 to give a two-dimensional perovskite [ (CH) 2 ) 3 NH 2 S] 2 PbBr 4 。
Characterization of compounds using single crystal X-ray diffraction: the results show that the compounds are at room temperatureCrystallization in monoclinic space group P2 1 C, unit cell constant of
β＝105.334(5)°，
The asymmetric unit comprises two organic thiazolidine cations, and one independent PbBr 6 Octahedron. The compound does not exhibit second harmonic and ferroelectric properties due to its presence in a centrally symmetric nonpolar space group.
Differential calorimetry (DSC) experiments characterize the phase change of the material, and the results show that the material has an endothermic peak at 327K and an exothermic peak at 322K.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (25)
1. A ferroelectric material with second harmonic effect is characterized in that the structural formula of the material is A m (MX n )(M'Y n' ) Wherein A is an organic cation, M and M' are each independently a metal cation, X and Y are each independently selected from the group consisting of halide, SCN - 、CN - 、N 3 - 、NO 3 - 、BF 4 - And ClO 4 - M is an integer of 1 to 5, n is an integer of 0 to 10, and n' is an integer of 3 to 11;
a is at least one of the cations selected from the following compounds: thiomorpholine, 2-methylthiomorpholine.
2. The ferroelectric material of claim 1, wherein the 2-methylthiomorpholine comprises (2R) -2-methylthiomorpholine and/or (2S) -2-methylthiomorpholine.
3. The ferroelectric material of claim 1, wherein M and M' are each independently selected from at least one of the following metal cations: k + 、Rb + 、Cs + 、Ag + 、Mn 2+ 、Fe 2+ 、Co 2+ 、Ni 2+ 、Cu 2+ 、Zn 2+ 、Cd 2+ 、Pb 2+ 、In 2+ 、In 3+ 、Sb 3+ And Bi 3+ At least one of (1).
4. The ferroelectric material of claim 1, wherein M and M' are each independently selected from Sb 3+ Or Bi 3+ 。
5. The ferroelectric material of claim 1, wherein X and Y are each independently selected from F - 、Cl - 、Br - 、I - 、SCN - 、CN - 、N 3 - 、NO 3 - 、BF 4 - And ClO 4 - At least one of (1).
6. The ferroelectric material of claim 1, wherein X and Y are each independently selected from Cl - And/or Br - 。
7. The ferroelectric material of any one of claims 1-6, wherein the ferroelectric material has a phase transition temperature of 100-600K; the entropy becomes 20-200J K -1 mol -1 (ii) a The enthalpy change is 2000-80000J mol -1 (ii) a The stable temperature is 400-600K; the ferroelectric polarization value is 0.3-20 μ C cm -2 。
8. The ferroelectric material of any one of claims 1-6, wherein the ferroelectric material has a phase transition temperature of 200-500K.
9. The ferroelectric material according to any one of claims 1 to 6Wherein the entropy of the ferroelectric material becomes 50-150J K -1 mol -1 。
10. The ferroelectric material of any one of claims 1-6, wherein the ferroelectric material has an enthalpy change of 5000-70000J mol -1 。
11. The ferroelectric material of any one of claims 1 to 6, wherein the ferroelectric material has a stabilization temperature of 450 to 550K.
12. The ferroelectric material of any one of claims 1-6, wherein the ferroelectric material has a ferroelectric polarization value of 0.4-10 μ C cm -2 。
13. The ferroelectric material of any one of claims 1-6, wherein the ferroelectric material is (C) 4 H 10 NS) 2 (SbCl 5 )(SbCl 3 ) Or (C) 4 H 10 NS) 2 (SbBr 5 )(SbBr 3 )。
14. A method of preparing a ferroelectric material having a second harmonic effect as in claim 1, the method comprising: contacting an inorganic metal salt with a source of organic cations in the presence of a polar solvent; wherein the anion in the inorganic metal salt is selected from halide ion and SCN - 、CN - 、N 3 - 、NO 3 - 、BF 4 - And ClO 4 - At least one of;
wherein the organic cation source may be selected from at least one of the hydrochloride salts of the following compounds: thiomorpholine, 2-methylthiomorpholine.
15. The method of claim 14, wherein 2-methylthiomorpholine comprises (2R) -2-methylthiomorpholine and/or (2S) -2-methylthiomorpholine.
16. The method of claim 14, wherein the ratio of the total molar amount of metal elements in the inorganic metal salt to the molar amount of the organic cation source is 1: (0.5-10);
and/or, the polar solvent is at least one selected from water, C1-C4 saturated monohydric alcohol, N-dimethylformamide, and acetonitrile.
17. The method of claim 14, wherein the ratio of the total molar amount of metal elements in the inorganic metal salt to the molar amount of the organic cation source is 1: (1-5);
and/or, the polar solvent is at least one selected from the group consisting of water, methanol, ethanol, and N, N-dimethylformamide.
18. The method according to any one of claims 14-17, wherein said contacting is by: a solution of an organic cation source is added to the inorganic metal salt.
19. The method of claim 18, wherein the solution of the organic cation source is obtained by dissolving the organic cation source in a polar solvent.
20. The method according to claim 18, wherein the concentration of the organic cation in the solution of the organic cation source is 0.5 to 5mol/L.
21. The method according to claim 18, wherein the organic cation is added at a rate of 0.01 to 0.5mmol/min relative to 1mmol of the metal element in the inorganic metal salt.
22. The method according to claim 18, wherein the organic cation is added at a rate of 0.05 to 0.2mmol/min with respect to 1mmol of the metal element in the inorganic metal salt.
23. The method of claim 14, wherein the contacting temperature is 20-120 ℃; the time is 1-5h.
24. The method of claim 14, wherein the contacting temperature is from 20 ℃ to 80 ℃.
25. The method of claim 14, wherein the contacting is for a time of 1 to 3 hours.
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