CN118339108A

CN118339108A - Chalcogenides and method for producing chalcogenides by liquid phase synthesis

Info

Publication number: CN118339108A
Application number: CN202280079616.5A
Authority: CN
Inventors: 木本祥纪; 稻留彻; 加藤拓也
Original assignee: Idemitsu Kosan Co Ltd
Current assignee: Idemitsu Kosan Co Ltd
Priority date: 2021-11-30
Filing date: 2022-11-30
Publication date: 2024-07-12

Abstract

A chalcogen perovskite, wherein the crystallite size τ1 calculated by using the scherrer equation in an X-ray diffraction spectrum obtained by measuring by X-ray diffraction is smaller than 40nm based on a diffraction peak having the largest peak height, and the proportion of the total area occupied by particles having a particle diameter of 10 μm or more measured by a microscopic method to the total area occupied by particles existing in the captured image range is 10% or less in the image range captured by a microscope.

Description

Chalcogenides and method for producing chalcogenides by liquid phase synthesis

Technical Field

The present invention relates to chalcogenides and methods for producing the same, compositions, powders, sintered bodies, films and methods for producing the same, methods for producing sheets, luminescent materials, luminescent devices, image sensors, photoelectric conversion devices, and bioluminescence markers.

Background

In recent years, quantum dots (semiconductor nanocrystals) have been attracting attention as a light-emitting device material of the next generation, which exhibit physical properties different from those of a bulk in light absorption characteristics or light emission characteristics, such as a change in light absorption wavelength (band gap energy) depending on particle size.

As the quantum dots, materials containing cadmium such as CdS, cdSe, cdTe are known, but development of materials containing no harmful metal such as cadmium is being advanced due to environmental problems.

As a material containing no harmful metal, chalcogenides having a perovskite crystal structure have been studied (for example, refer to non-patent documents 1 to 2 and patent document 1). For example, non-patent documents 1 to 2 disclose chalcogenides synthesized by solid-phase synthesis.

The synthesis of microparticles by solid phase synthesis is a well-known method, but has problems such as easy mixing of impurities during synthesis, and significant aggregation of particles. Therefore, particles obtained by the solid-phase synthesis method are not easily miniaturized in particle diameter, and the particle diameter and shape are difficult to control, so that the particle size distribution is easily widened.

In addition, in the solid-phase synthesis method, a substance having a micrometer size is generally easily obtained, and when the substance is further pulverized to form nanoparticles, a large number of defects are generated on the surface and inside of the particles, and therefore the fluorescence intensity is significantly reduced.

In contrast, the liquid phase synthesis method attracts attention as a method capable of eliminating the above-described problem of the solid phase synthesis method in the synthesis of fine particles.

As an example using a liquid phase synthesis method, for example, patent document 1 discloses a method for producing semiconductor nanocrystals, in which a 1 st metal precursor, a 2 nd metal precursor, and a chalcogen element precursor are heated at a temperature of about 100 ℃ to 400 ℃ in the presence of an organic solvent and a ligand compound.

Prior art literature

Patent literature

Patent document 1: US2019/0225883

Non-patent literature

Non-patent document 1: V.K. Ravi et al ,″Colloidal BaZrS₃ chalcogenide perovskite nanocrystals for thin film device fabrication″,The Royal Society of Chemistry,Nanoscale,2021,, volume 13, pages 1616-1623

Non-patent document 2: s. Filipsone et al ,″High densification ofBaZrS₃ powder inspired by the cold-sintering process″,Journal of Materials Research,2021,, volume 36, pages 4404-4412

Disclosure of Invention

The present inventors produced chalcogenides based on the liquid phase synthesis method of chalcogenides disclosed in patent document 1. The crystal structure was examined, and as a result, it was different from the crystal structure obtained by the solid phase synthesis using JCPDS cards.

The purpose of the present invention is to provide a chalcogen perovskite which can easily obtain desired light absorption characteristics or light emission characteristics.

The present invention also aims to provide a method for producing a chalcoperovskite having a crystal structure similar to that of solid phase synthesis even by liquid phase synthesis.

According to the present invention, the following chalcogen perovskite, a method for producing the same, and the like are provided.

1. A chalcogen perovskite, wherein the crystallite size τ1 calculated by using the scherrer equation in an X-ray diffraction spectrum obtained by measuring by X-ray diffraction is smaller than 40nm based on a diffraction peak having the largest peak height, and the proportion of the total area occupied by particles having a particle diameter of 10 μm or more measured by a microscopic method to the total area occupied by particles existing in the captured image range is 10% or less in the image range captured by a microscope.

2. The chalcogen perovskite according to claim 1, wherein the crystallite size τ2 calculated by the wilhelmy-hall formula is 34.5nm or less based on an X-ray diffraction spectrum obtained by X-ray diffraction measurement.

3. The chalcopyrite according to claim 2, wherein the crystallite size τ2 is 30nm or less.

4. A chalcopyrite according to any of claims 1 to 3, wherein the crystallite size τ1 is less than 17.5nm.

5. The chalcopyrite according to any one of claims 1 to 4, wherein the chalcoperovskite has a composition represented by the following formula (101) or (102),

ABCh₃…(101)

A′₂A_n-1B_nCh_3n+1…(102)

(In the formulae (101), (102), A, A ' is Sr, ba or a combination thereof, B is Zr, hf or a combination thereof, ch is S, se, te or a combination thereof.) in the formula (102), n is an integer of 1 or more and 10 or less, A, A ' may be the same as or different from each other in the formula (102), the chalcogen perovskite may be a solid solution in which a part or all of A, A ', B, ch is replaced with another element in the composition represented by the formula (101) or (102).

6. The chalcopyrite according to any one of claims 1 to 5, wherein particles of the chalcopyrite are surface-modified with ligands.

7. A composition comprising the chalcogen perovskite according to any one of 1 to 6 dispersed in a dispersion medium.

8. The composition according to 7, which is a dispersion using a liquid dispersion medium as the dispersion medium.

9. The composition according to claim 8, wherein the liquid dispersion medium is at least one selected from the group consisting of water, esters, ketones, ethers, alcohols, glycol ethers, organic solvents having amide groups, organic solvents having nitrile groups, organic solvents having carbonate groups, organic solvents having halogenated hydrocarbon groups, organic solvents having hydrocarbon groups, and dimethyl sulfoxide.

10. The composition according to 7, which is a sheet using a solid dispersion medium as the dispersion medium.

11. The composition according to claim 10, wherein the solid dispersion medium is at least one selected from the group consisting of polyvinyl butyral, polyvinyl acetate, and silicone and derivatives thereof.

12. A powder comprising the chalcopyrite according to any one of 1 to 6.

13. The powder according to claim 12, wherein the primary particles or secondary particles of the chalcogen perovskite are surface-modified with ligands.

14. A sintered body obtained by sintering the powder according to 12 or 13.

15. A film comprising the chalcopyrite according to any one of 1 to 6.

16. The method for producing a film according to 15, wherein the dispersion according to 8 or 9 is formed into a film by a coating method, a spray method, a doctor blade method or an inkjet method.

17. The method for producing a thin film according to 15, wherein the powder of chalcogen perovskite according to 12 or 13 is formed into a film by a sputtering method or a vacuum evaporation method.

18. The method for producing a sheet according to 10, wherein the dispersion liquid according to 8 or 9 is dried after being coated in a sheet form.

19. A luminescent material comprising the chalcogen perovskite according to any one of claims 1 to 6.

20. A light-emitting device, an image sensor, a photoelectric conversion device, or a bioluminescent label comprising the chalcogen perovskite according to any one of 1 to 6.

21. A process for producing a chalcoperovskite, comprising reacting a complex compound having a 1 st metal atom with a complex compound having a2 nd metal atom in a liquid phase,

The complex compound having a 1 st metal atom and the complex compound having a2 nd metal atom have a ligand not containing an oxygen atom (O) and a halogen atom (X) as the coordinating atoms.

22. The production method according to claim 21, wherein the complex compound having a1 st metal atom and the complex compound having a 2 nd metal atom each have a ligand coordinated by an atom selected from the group consisting of a nitrogen atom (N), a sulfur atom (S), a selenium atom (Se), a tellurium atom (Te), a carbon atom (C) and a phosphorus atom (P).

23. The production method according to claim 21 or 22, wherein the metal atom of the complex compound having a1 st metal atom is at least one of Sr and Ba, and the metal atom of the complex compound having a 2nd metal atom is at least one of Zr and Hf.

24. The production method according to claim 23, wherein at least one selected from the group consisting of Ti, ca, and Mg is further used in at least one of the metal atom of the complex compound having the 1 st metal atom and the metal atom of the complex compound having the 2 nd metal atom.

25. The production method according to any one of claims 21 to 24, wherein the ligand is a dithiocarbamate, xanthate, trithiocarbamate, dithioester, thiolate, sulfide, or a compound in which part or all of sulfur atoms contained in them is replaced with selenium atoms or tellurium atoms, an alkylamine, an arylamine, a trialkylsilylamine, a nitrogen-containing aromatic ring, an alkane, an unsaturated hydrocarbon ring, or a group derived from the unsaturated hydrocarbon ring, a cyano group, a trialkylphosphine, a triarylphosphine, or a diphosphine.

26. The production method according to any one of claims 21 to 25, wherein the complex compound having a1 st metal atom and the complex compound having a2 nd metal atom are binuclear complex compounds as a single compound.

27. The production method according to claim 26, wherein the 1 st metal atom and the 2 nd metal atom are bonded via a ligand which coordinates with a sulfur atom, a selenium atom or a tellurium atom.

28. The production process according to any one of claims 21 to 27, wherein the chalcopyrite has a composition represented by the following formula (101) or (102),

ABCh₃…(101)

A′₂A_n-1B_nCh_3n+1…(102)

29. The production method according to any one of claims 21 to 28, wherein a chalcogen compound is further added.

30. The method according to any one of claims 21 to 29, wherein an amine compound is further added.

31. The production method according to any one of claims 21 to 30, wherein the temperature of the liquid phase is set to room temperature to 450 ℃.

32. The production method according to claim 31, wherein the temperature of the liquid phase is set to 120 ℃ to 360 ℃.

33. The production method according to any one of claims 21 to 32, wherein the reaction is caused by adding a2 nd raw material to a 1 st raw material containing at least a solvent, among raw material components containing the complex compound having a 1 st metal atom, the complex compound having a2 nd metal atom, and the solvent, wherein the 2 nd raw material contains at least a raw material component not contained in the 1 st raw material among the raw material components.

34. The production method according to claim 33, wherein the reaction is caused by adding the 2 nd raw material to the 1 st raw material in a state where at least one of the 1 st raw material and the 2 nd raw material is heated in advance.

35. The production method according to claim 33, wherein the reaction is caused by heating the 1 st raw material and the 2 nd raw material after adding the 2 nd raw material to the 1 st raw material.

36. The production method according to claim 35, wherein a dispersion in which the complex compound having the 1 st metal atom and the complex compound having the 2 nd metal atom are dispersed in the dispersion medium is formed into a film by a coating method, a spray method, a doctor blade method or an inkjet method, and the obtained coating film is subjected to a heat treatment.

37. The production method according to any one of claims 21 to 32, wherein the reaction is caused by simultaneously mixing the complex compound having a1 st metal atom, the complex compound having a2 nd metal atom, and at least 1 of a chalcogen compound and an amine compound.

38. The production method according to claim 37, wherein the reaction is caused by allowing at least 1 of the complex having a1 st metal atom, the complex having a2 nd metal atom, and the chalcogen compound and the amine compound to flow in separate fluids, and causing the fluids to flow together at the same time.

39. The production method according to claim 37 or 38, wherein at least 1 of the following components is heated in advance: the complex compound having a1 st metal atom; the complex compound having a metal atom of 2 nd; and at least 1 of the chalcogen compound and the amine-based compound.

According to the present invention, it is possible to provide a chalcoperovskite which can easily obtain desired light absorption characteristics or light emission characteristics. Further, according to the present invention, a method for producing a chalcoperovskite having a crystal structure similar to that of solid phase synthesis can be provided even by liquid phase synthesis.

Brief description of the drawings

Fig. 1 is a diagram for explaining a relationship between a crystallite size d10 and a particle diameter d 20.

Fig. 2 is an X-ray diffraction spectrum of the chalcogen perovskite manufactured in example 1 and example 2.

Fig. 3A is a graph showing diffraction peaks based on the X-ray diffraction spectrum of example 1, and an approximate straight line prepared using the wilhelmson-hall formula.

Fig. 3B is a graph showing diffraction peaks based on the X-ray diffraction spectrum of example 2, and an approximate straight line prepared using the wilhelmson-hall formula.

Fig. 4 is an SEM image (25 ten thousand times) of the composition obtained in example 1.

Fig. 5 is an SEM image (25 ten thousand times) of the composition obtained in example 1.

FIG. 6 is a STEM image (20 ten thousand times) of the composition obtained in example 2.

Fig. 7 is a STEM image (40 ten thousand times) of the composition obtained in example 2.

Detailed Description

The following describes modes for carrying out the invention.

In the present specification, "x to y" means a numerical range of "x or more and y or less". The upper limit and the lower limit described for the numerical range may be arbitrarily combined.

Further, 2 or more embodiments that do not violate each other among the embodiments of the present invention described below can be combined, and the combined embodiment of 2 or more embodiments is also an embodiment of the present invention.

The chalcogen perovskite according to one form of the present invention is characterized in that: the crystallite size τ1 calculated using the scherrer equation (Scherror) is less than 40nm. In the image range photographed by a microscope, the proportion of the total area occupied by particles having a particle diameter of 10 μm or more measured by a microscope to the total area occupied by particles existing in the photographed image range is 10% or less.

In the following description, the "crystallite size" refers to the diameter d10 of the crystallites 10 calculated by the scherrer equation or the wilamason-Hall equation (Williamson-Hall equation) described below, and the diameter d20 of the polycrystal 20 formed by integrating a plurality of crystallites 10 is referred to as "particle size" (see fig. 1).

[ Crystallite size τ1]

The crystallite size τ1 is a value calculated by the scherrer equation represented by the following equation (a) based on a diffraction peak having the largest peak height in an X-ray diffraction spectrum obtained by X-ray diffraction measurement.

τ1＝Kλ/βcosθ…(a)

Θ: diffraction angle of maximum peak [ rad ]

Beta: half peak width of maximum peak [ rad ]

K: form factor

Lambda: wavelength of X-ray

Τ1: crystallite size

The X-ray diffraction measurement was performed by the method described in examples.

As for chalcogenides, for example, there are substances whose absorption spectrum overlaps with the emission spectrum in a partial wavelength region as in BaZrS ₃ described later. In a wavelength region where the absorption spectrum overlaps with the emission spectrum, a part of the emission emitted from the particles is reabsorbed (self-reabsorption) by particles in the vicinity thereof, whereby the emission efficiency is lowered.

The chalcogenides of this form pass crystallite sizes τ1 of less than 40nm and the particle sizes are small enough to inhibit self-resorption. Therefore, by applying the chalcogen perovskite of the present form to a light-emitting material, good light-emitting efficiency can be exhibited, and excellent light-emitting characteristics can be obtained.

In addition, if the particle diameter is reduced to the nano-scale, the excited carriers (electrons and holes) are spatially confined, and the carriers are less likely to be scattered (carrier confinement effect).

The chalcogenides of this form have a crystallite size τ1 of less than 40nm, and the movable range of the carriers excited and confined is narrowed, so that the probability of recombination in the particles is improved. Therefore, by applying the chalcogen perovskite of the present form to a light-emitting material, the light-emitting efficiency can be improved, and excellent light-emitting characteristics can be obtained.

Further, by coating the chalcopyrite of the present form (core-shell formation) with a material having a larger band gap than the chalcoperovskite, the carrier confinement effect can be enhanced.

In general, when the particle diameter is reduced to the nano-scale, the band structure (energy level) of the particles becomes discrete, and the value of the optical band gap changes depending on the particle size (quantum size effect). In this case, the value of the band gap gradually increases as the particle diameter decreases, and if the value is smaller than a predetermined particle diameter, the value of the band gap rapidly increases.

The chalcogenides of this form can exhibit a higher band gap by crystallite size τ1 of less than 40nm than chalcogenides of particle size greater than it. In particular, when the crystallite size τ1 is 30nm or less, the effect is large. Therefore, by changing the crystallite size τ1 of the particles in a range of less than 40nm, the band gap can be set to a desired value.

By controlling the band gap of the chalcogen perovskite of the present embodiment to be in an appropriate range, and applying it to, for example, a solar cell or a light-emitting material, it is possible to control the band gap so as to exhibit light absorption characteristics and light emission characteristics (light emission wavelengths) suitable for each use.

The crystallite size τ1 of the chalcogen perovskite may be 35nm or less, 30nm or less, 25nm or less, 20nm or less, less than 17.5nm or less, 17nm or less, 15nm or less, 13nm or less, 12nm or less, 11.5nm or less, or 10nm or less.

The lower limit of the crystallite size τ1 of the chalcogen perovskite is not particularly limited, but may be, for example, 1nm or more from the viewpoint of convenience in the production process.

In one embodiment, the chalcogen perovskite has a maximum diffraction peak at 2θ=25.0±1deg in the X-ray diffraction spectrum obtained by the above-described measurement by X-ray diffraction. The crystallite size τ1 calculated based on the diffraction peak (2θ=25.0±1 deg) is smaller than 40nm.

The crystallite size τ1 calculated based on the diffraction peak of 2θ=25.0±1deg may be 35nm or less, 30nm or less, 25nm or less, 20nm or less, less than 17.5nm, 17nm or less, 15nm or less, 13nm or less, 12nm or less, 11.5nm or less, or 10nm or more, or may be 1nm or more.

The chalcogen perovskite of the present embodiment improves uniformity of a film or sheet formed by using the chalcogen perovskite of the present embodiment by setting a ratio of a total area occupied by particles having a particle diameter of 10 μm or more measured by a microscopic method to a total area occupied by particles existing in a captured image range to 10% or less in an image range captured by a microscope.

In addition, in the image range captured by a microscope, the nozzle clogging at the time of applying the ink produced using the chalcogen perovskite of the present embodiment can be suppressed by setting the ratio of the total area occupied by particles having a particle diameter of 10 μm or more measured by a microscope to the total area occupied by particles existing in the captured image range to 10% or less.

In addition, in the image range captured by a microscope, the ratio of the total area occupied by particles having a particle diameter of 10 μm or more measured by a microscope to the total area occupied by particles existing in the captured image range is set to 10% or less, whereby the emission spectrum distribution as a quantum dot is narrowed. Therefore, by applying the chalcogen perovskite of the present form to a light-emitting material, color unevenness of light emission is suppressed, and furthermore, color purity is improved and monochromaticity is improved.

Microscopy refers to a method in which the size and number of particles are measured directly on an image of an optical microscope or an electron microscope. Examples of the diameter to be used as an index for evaluating the particle size include a fermi diameter, a projected area circle equivalent diameter (Heywood diameter), a martin diameter (MARTIN DIAMETER), and a directional maximum diameter (Krummbein diameter), but from the viewpoint of ease of calculation based on image analysis, a diameter to be evaluated using the projected area circle equivalent diameter as an index is used as the particle size.

In the case of measuring the particle size by a microscopic method, the particle size may be different depending on the measurement place. In view of this, in the case of measuring the particle size by a microscopic method, image capturing is performed at a plurality of places, and particle size measurement is performed on each of the plurality of captured images obtained thereby. In addition, when the particle size is measured by a microscope method, image capturing is performed at a plurality of places, and the proportion of the total area occupied by particles having a particle size of 10 μm or more is calculated for each of the plurality of captured images. In the case of measuring the particle size distribution by a microscope method, the imaging range is set to be a range containing 100 or more particles.

The method for calculating the "ratio of the total area occupied by particles having a particle diameter of 10 μm or more measured by a microscope method to the total area occupied by particles existing in the captured image range" is described in detail in examples.

In one embodiment, the crystallite size τ2 calculated by the wilhelmson-hall formula represented by the following formula (b) is 34.5nm or less based on an X-ray diffraction spectrum obtained by X-ray diffraction measurement.

γcosθ＝ε(2sinθ)+Kλ/τ2…(b)

Θ: diffraction angle of diffraction peak [ rad ]

Beta: half-width of diffraction peak [ rad ]

K: form factor

Lambda: wavelength of X-ray

Epsilon: lattice strain

Τ2: crystallite size

In the above formula (b), the half-width γ of the diffraction peak is assumed to be the sum of the half-width (β _size) due to the crystallite size and the half-width (β _strain) due to the lattice strain.

The calculation of the crystallite size τ2 based on the above formula (b) was performed according to the procedure described in the examples.

The effect of having a crystallite size τ2 of 34.5nm or less is similar to that of having a crystallite size τ1 of 40nm or less.

The crystallite size τ2 of the chalcogen perovskite may be 32nm or less, 30nm or less, 25nm or less, 20nm or less, 18nm or less, 15nm or less, 14.5nm or less, or 10nm or less.

The lower limit of the crystallite size τ2 of the chalcogen perovskite is not particularly limited, but may be, for example, 1nm or more from the viewpoint of convenience in the production process.

The chalcogen perovskite according to one embodiment is a compound containing a chalcogen element (group 16 element (S, se or Te) other than oxygen) having a perovskite-type crystal structure, and contains two or more metal elements such as a transition metal element and an alkaline earth metal element as constituent components of the perovskite-type crystal structure in addition to the chalcogen element.

In one embodiment, the chalcogen perovskite has a composition represented by the following formula (101) or (102), for example.

ABCh₃…(101)

A'₂A_n-1B_nCh_3n+1…(102)

In the formulas (101) and (102), A, A' are Sr, ba or a combination thereof in any proportion, B is Zr, hf or a combination thereof in any proportion, and Ch is S, se, te or a combination thereof in any proportion.

In the formula (102), n is an integer of 1 to 10.

In formula (102), A and A' may be the same or different from each other.

In one embodiment, the chalcogenides may be solid solutions in which some or all of A, A', B, ch are replaced with other elements in the composition represented by formula (101) or (102).

The chalcogenides (ABCh ₃) represented by the formula (101) show, for example, a crystal structure of cubic perovskite, tetragonal perovskite, orthorhombic perovskite, or double perovskite.

The chalcogen perovskite (A' ₂A_n-1B_nCh_3n+1) represented by the formula (102) shows, for example, the crystal structure of Ruddlesden-pop er type layered perovskite.

In one embodiment, particles of chalcogen perovskite are surface modified with ligands.

The particles of the chalcoperovskite according to the present embodiment, which have been surface-modified with a ligand, can be easily dispersed in a liquid dispersion medium or a solid dispersion medium such as a polymer compound.

The kind of the ligand for surface modification of the chalcogen perovskite is not limited, and it is generally applicable to dispersion of nanoparticles. Examples of the ligand for surface modification include one or more selected from the group consisting of oleylamine, oleic acid, dodecylmercaptan, and trioctylphosphine.

The dispersion medium for dispersing the chalcoperovskite of the present embodiment, which has been surface-modified with the ligand, may be a liquid dispersion medium or a solid dispersion medium.

The liquid dispersion medium (hereinafter, referred to as a liquid dispersion medium) may be, for example, a dispersion liquid in which various solvents selected from nonaqueous solvents such as toluene and hexane and water, or other components other than chalcogenides are dispersed in these solvents.

The solid dispersion medium (hereinafter referred to as a solid dispersion medium) may be, for example, a polymer compound such as polyethylene.

For example, in order to disperse particles of chalcoperovskite synthesized by the solid phase synthesis method in the above-described dispersion medium, it is preferable to perform surface modification by modifying the particle surface with a ligand, so as to improve dispersibility in various dispersion media.

In contrast, in the case of synthesizing particles of chalcogen perovskite by the liquid phase synthesis method, the chalcogen perovskite can be obtained as particles surface-modified with ligands by carrying out the synthesis reaction in a state in which ligands are previously present in a liquid phase of a reaction liquid which is a liquid phase synthesis method.

(Composition)

The composition according to one embodiment includes the chalcogen perovskite according to the present embodiment dispersed in a dispersion medium.

The composition according to one embodiment includes the chalcogen perovskite of the present embodiment, which is surface-modified with a ligand, dispersed in a dispersion medium.

As described above, the chalcoperovskite surface-modified with the ligand can be easily dispersed in a liquid dispersion medium, a solid dispersion medium such as a polymer compound, or the like. Therefore, the composition according to the present embodiment has excellent properties as a composition in which the chalcogen perovskite is uniformly dispersed in the dispersion medium.

One embodiment relates to a composition that is a dispersion using a liquid dispersion medium as a dispersion medium.

In the present specification, the dispersion liquid of the chalcogen perovskite means a substance in which the chalcogen perovskite is dispersed in a liquid dispersion medium.

"Dispersed chalcogenides" refers to a state in which the chalcogenides are floating or suspended in a liquid dispersion medium, and a portion of the chalcogenides may also precipitate in the dispersion.

For the purpose of improving various properties such as dispersibility, luminescence properties, film forming properties, and the like of the chalcoperovskite, the dispersion of the chalcoperovskite may contain, in addition to the chalcoperovskite, an acid, a base, a binder material, and the like as additives.

The sizes of the primary particles and the secondary particles of the chalcogen perovskite dispersed in the dispersion are not particularly limited. The size of the primary particles in the dispersion is, for example, preferably 5 to 1000nm, more preferably 5 to 100nm, and even more preferably 5 to 20nm.

The type of the liquid dispersion medium used for the dispersion of the chalcoperovskite is not particularly limited, and examples thereof include: water; methyl formate, ethyl formate, propyl formate, pentyl formate, methyl acetate, ethyl acetate, amyl acetate, and the like; ketones such as gamma-butyrolactone, acetone, dimethyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, and methylcyclohexanone; ethers such as diethyl ether, methyl tertiary butyl ether, diisopropyl ether, dimethoxymethane, dimethoxyethane, 1, 4-dioxane, 1, 3-dioxolane, 4-methyldioxolane, tetrahydrofuran, methyltetrahydrofuran, anisole, phenetole and the like; alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, t-butanol, 1-pentanol, 2-methyl-2-butanol, methoxypropanol, diacetone alcohol, cyclohexanol, 2-fluoroethanol, 2-trifluoroethanol, and 2, 3-tetrafluoro-1-propanol; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, triethylene glycol dimethyl ether, and the like; an organic solvent having an amide group such as N-methyl-2-pyrrolidone, N-dimethylformamide, acetamide, and N, N-dimethylacetamide; organic solvents having a nitrile group such as acetonitrile, isobutyronitrile, propionitrile, methoxyacetonitrile and the like; organic solvents having carbonate groups such as ethylene carbonate and propylene carbonate; organic solvents having halogenated hydrocarbon groups such as methylene chloride and chloroform; organic solvents having a hydrocarbon group such as n-pentane, cyclohexane, n-hexane, benzene, toluene, and xylene; dimethyl sulfoxide, and the like.

As the liquid dispersion medium for the dispersion liquid of the chalcoperovskite, one kind may be used alone, or two or more kinds may be used in combination.

The use of the chalcoperovskite dispersion is not particularly limited.

For example, the composition can be used as a film-forming material for forming a film by a solution film-forming method such as a coating method, a spraying method, or a doctor blade method, or as a composite composition obtained by compositing a dispersion of chalcogen perovskite with a solid dispersion medium.

Films and compositions produced using the chalcogen perovskite dispersion are useful for, for example, production of various devices described below.

The method for producing the chalcopyrite according to one embodiment of the present invention described above will be described below.

The method for producing a chalcoperovskite according to one embodiment of the present invention is characterized by: reacting a complex compound having a1 st metal atom and a complex compound having a 2 nd metal atom in a liquid phase, the complex compound having a1 st metal atom and the complex compound having a 2 nd metal atom having a ligand free of an oxygen atom (O) and a halogen atom (X) as the coordinating atoms.

The present inventors have found that, in the case of synthesizing a chalcoperovskite in a liquid phase, for example, if a component containing a halogen atom (X) such as a halide or a component containing an oxygen atom (O) such as an acetate is mixed in the liquid phase synthesis, the reaction may be hindered, and the purity and crystal structure of the chalcoperovskite as a target may be affected.

Examples of the halogen atom (X) include: fluorine atom (F), chlorine atom (C1), bromine atom (Br), iodine atom (I), etc.

In this embodiment, the complex compound having the 1 st metal atom and the complex compound having the 2 nd metal atom, which have a ligand containing no oxygen atom and no halogen atom as the coordinating atoms, are reacted in the liquid phase, whereby the liquid phase synthesis reaction can be performed without causing a component containing an oxygen atom such as a metal acetate or a component containing a halogen atom such as a metal halide to exist in the liquid phase. This suppresses the reaction between the constituent elements of the chalcogen perovskite in the liquid phase and the oxygen atoms and the halogen atoms. As a result, the same crystal structure as in solid phase synthesis can be exhibited.

Hereinafter, a description will be given of a method for producing a complex compound having the 1 st metal atom and a complex compound having the 2 nd metal atom as starting materials, and a chalcoperovskite.

[ Coordination Compound having the 1 st Metal atom and coordination Compound having the 2 nd Metal atom ]

The ligand of the complex compound having the 1 st metal atom and the complex compound having the 2 nd metal atom used in this form is not particularly limited, except that an oxygen atom and a halogen atom are not contained as the coordinating atoms. Examples of the ligand include ligands coordinated by an atom selected from the group consisting of nitrogen atom (N), sulfur atom (S), selenium atom (Se), tellurium atom (Te), carbon atom (C) and phosphorus atom (P).

Examples of the ligand that coordinates with a nitrogen atom include: alkylamines (NR ₂) such as amines, dimethylamine, diethylamine, methylethylamine, etc.; arylamine (NHAr) such as phenylamine; trialkylsilylamines (N (SiR ₃)₂)) such as silylamines and trimethylsilylamines, nitrogen-containing aromatic rings such as pyrazoles, and the like.

Examples of the ligand that coordinates with a sulfur atom include: dithiocarbamate (dithiocarbamate) (S ₂CNR₂), xanthate (xanthonate) (S ₂ COR), trithiocarbamate (trithiocarbamate) (S ₂ CSR), dithioester (dithioester) (S ₂ CR), thiolate (thiolate) (SR), and the like.

Examples of the ligand which coordinates with a selenium atom or a tellurium atom include compounds in which a part or all of the sulfur atoms of the ligand which coordinates with the sulfur atom are replaced with selenium atoms or tellurium atoms.

The complex compound having the 1 st metal atom and the complex compound having the 2 nd metal atom may be a single compound (binuclear complex compound). A single compound (binuclear complex) refers to a compound having both the 1 st metal atom and the 2 nd metal atom in 1 complex as the central metal ion of the complex. Preferably, the 1 st metal atom and the 2 nd metal atom may be bonded via a ligand coordinated with a sulfur atom, a selenium atom, or a tellurium atom.

Examples of the binuclear complex in which the ligand is coordinated by a sulfur atom include heteronuclear bimetallic mercaptides and heteronuclear bimetallic sulfides. In these binuclear complex compounds, the 1 st metal atom and the 2 nd metal atom are bonded via a thiolate or sulfide (a ligand coordinated by a sulfur atom) as a ligand.

As the binuclear complex in which the ligand is coordinated by a selenium atom or a tellurium atom, a complex in which part or all of the sulfur atoms in the binuclear complex in which the ligand is coordinated by a sulfur atom are substituted by a selenium atom or a tellurium atom can be exemplified.

Examples of the ligand that coordinates with a carbon atom include: alkanes such as methyl and ethyl; unsaturated hydrocarbon rings such as cyclopentadiene, cyclooctadiene, indene, etc., or benzyl groups, other groups derived from the above unsaturated hydrocarbon rings; cyano (CN), and the like.

Examples of the ligand that coordinates with the phosphorus atom include: trialkyl phosphines (PR ₃) such as trioctylphosphine and tricyclohexylphosphine; triarylphosphines (PAr ₃) such as triphenylphosphine and tris (o-tolyl) phosphine; diphosphines (R ₂P-(CH₂)_m-PR₂), and the like.

The ligand may be a derivative of the above ligand.

In the general formulae, R is a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an unsaturated hydrocarbon. In the case where one ligand contains 2 or more R, R may be the same or may be different from each other.

Ar is an aryl group having 6 to 20 carbon atoms which may have a substituent such as a phenyl group, a naphthyl group or an anthryl group. Examples of the substituent include an alkyl group having 1 to 10 carbon atoms. In the case where one ligand contains 2 or more Ar, ar may be the same or may be different from each other.

M is an integer of 1 to 10.

Among the above ligands, a ligand that coordinates with a nitrogen atom or a ligand that coordinates with a sulfur atom is preferable.

Further, a ligand having a structure selected from the following formulae (1) to (7) is preferable.

S₂CNR^a ₂ (1)

S₂COR (2)

S₂CSR^a (3)

S₂CR^a (4)

SR^a(5)

NR^a ₂ (6)

N(SiR^a ₃)₂ (7)

( Wherein R ^a is a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms or an unsaturated hydrocarbon group having 1 to 20 carbon atoms. In the case where one ligand has a plurality of R ^a, a plurality of R ^a may be the same or different )

Examples of the saturated hydrocarbon group and unsaturated hydrocarbon include: alkyl group having 1 to 20 carbon atoms, cycloalkyl group having 3 to 20 carbon atoms, alkenyl group having 2 to 20 carbon atoms, alkynyl group having 2 to 20 carbon atoms, cycloalkenyl group having 3 to 20 carbon atoms, cycloalkynyl group having 3 to 20 carbon atoms, cyclodienyl group having 3 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms.

The saturated hydrocarbon group and the unsaturated hydrocarbon may have a substituent. Examples of the substituent include an alkyl group having 1 to 10 carbon atoms.

In one form, the ligand is preferably a compound represented by the above formula (1). R ^a in formula (1) is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 2 to 6 carbon atoms.

The ligands used in this form can be synthesized according to conventional methods. In addition, commercially available compounds may also be used.

The metal atom of the complex compound having the 1 st metal atom is a metal atom selected from alkaline earth metal elements, and the metal atom of the complex compound having the 2 nd metal atom is a metal atom selected from transition metal elements.

In one embodiment, the metal atom of the complex compound having the 1 st metal atom is at least one of Sr and Ba, and the metal atom of the complex compound having the 2 nd metal atom is at least one of Zr and Hf.

At least one of the metal atom of the complex compound having the 1 st metal atom and the metal atom of the complex compound having the 2 nd metal atom may further contain at least one selected from Ti, ca and Mg.

The complex compound having the 1 st metal atom and the complex compound having the 2nd metal atom can be synthesized by a known method by selecting a raw material component according to the kinds of the metal atom and the ligand each having. In addition, commercially available metal complex compounds can also be used.

Hereinafter, as an example of a method for synthesizing a complex compound having a 1 st metal atom and a complex compound having a 2 nd metal atom, a method for synthesizing a metal complex compound (M (S ₂CNR₂)_X) having a ligand (S ₂CNR₂) represented by formula (1) will be described.

First, as a metal source (M) which is a source of metal atoms of the metal complex, for example, at least one selected from Ba, sr, ca, mg, zr and Hf or a salt thereof is dissolved in a solvent such as water.

The solvent is not particularly limited as long as it is a solvent capable of dissolving the metal raw material (M), and may be an organic solvent, for example.

Then, ammonia or an amine compound is added to the solution in which the metal raw material is dissolved as a source of nitrogen (N) contained in the ligand of the complex to be synthesized, and the mixture is stirred.

The amine compound may be a primary amine or a secondary amine, and the type of the substituted hydrocarbon group or the like in the amine compound is not particularly limited.

Then, a supply source of sulfur (S) contained in the complex ligand of the synthesis target is further added to the solution to which the nitrogen (N) supply source is added, and stirring is performed.

As a supply source of sulfur (S), CS ₂ is typically used, but other compounds can be used depending on the composition of the ligand of the complex to be synthesized. Note that CSe ₂、CTe₂ can be used when Se or Te is contained instead of sulfur (S).

Then, the solid formed by stirring or the precipitate precipitated in the solution is separated by a known method, whereby the target metal complex can be obtained.

[ Method for producing chalcoperovskite ]

In this form, the chalcogen perovskite is produced by reacting the complex compound having the 1 st metal atom and the complex compound having the 2 nd metal atom in a solvent.

The solvent may be appropriately selected from the viewpoints of the solubility of the complex compound having the 1 st metal atom and the complex compound having the 2 nd metal atom, the efficiency of H ₂ S generation, and the like.

Examples of the solvent include: saturated aliphatic hydrocarbons, unsaturated aliphatic hydrocarbons, aromatic hydrocarbons, nitrogen-containing heterocyclic compounds, alcohols, aldehydes, carboxylic acids, primary amines, secondary amines, tertiary amines, phosphine compounds, thiols, and the like.

As the solvent, a solvent having a higher boiling point is preferably used in view of the fact that the liquid phase is heated to a high temperature of 300 ℃ or higher in some cases in a liquid phase synthesis stage described later.

For example, olefins having 10 to 30 carbon atoms such as octadecene have a high boiling point and are therefore suitable for use as solvents.

In one embodiment, in addition to the complex compound having the 1 st metal atom and the complex compound having the 2 nd metal atom, a chalcogen compound can be further added to the liquid phase. For example, when neither the ligand of the complex having the 1 st metal atom nor the ligand of the complex having the 2 nd metal atom has a chalcogen element such as sulfur (S), or when the chalcogen element of the ligand is insufficient, the chalcogen element compound is added to the liquid phase, whereby the composition of the chalcogen perovskite as the target substance can be adjusted.

As the chalcogen compound, a compound containing no oxygen atom (O) or halogen atom (X) is preferably used. Examples include: sulfide such as sulfur or carbon disulfide (CS ₂), hydrogen sulfide (H ₂ S), selenium or selenide, tellurium or telluride, hexanethiol, octanethiol, decanethiol, dodecanethiol (n-dodecanethiol, t-dodecanethiol), hexadecanethiol, mercaptopropylsilane, dialkylthiourea (s=c (NR ₂)₂), sulfur-trioctylphosphine (trioctylphosphine sulfide; S-TOP), sulfur-tributylphosphine (S-TBP), sulfur-triphenylphosphine (S-TPP), sulfur-trioctylamine (S-TOA), bis (trimethylsilyl) sulfide, ammonium sulfide, sodium sulfide, selenium-trioctylphosphine (Se-TOP), selenium-tributylphosphine (Se-TBP), selenium-triphenylphosphine.

Among them, thiourea such as dialkylthiourea (s=c (NR ₂) has a higher boiling point than carbon disulfide (CS ₂), for example, and thus can be suitably used as a chalcogen compound.

In one embodiment, in addition to the above-described complex compound having the 1 st metal atom and complex compound having the 2 nd metal atom, an amine-based compound can be further added to the liquid phase. The amine compound functions as a reaction initiator. The amine compound may be used as the solvent.

As the amine compound, a compound containing no oxygen atom (O) or halogen atom (X) is preferably used. Examples include: alkylamines having 1 alkyl group such as oleylamine, cetyl amine, and stearyl amine; dialkylamine having 2 alkyl groups of 1 to 30 carbon atoms; trialkylamine having 3 alkyl groups of 1 to 30 carbon atoms (e.g., trioctylamine), and the like.

From the viewpoint of sufficiently functioning as a reaction initiator for the ligand and the metal component, the amine compound is preferably added in an amount equal to or more than the total amount of the number of ligands contained in the complex having the 1 st metal atom and the complex having the 2 nd metal atom added to the liquid phase.

In addition, from the viewpoint of functioning as a surfactant attached to the particle surface of the finally obtained chalcoperovskite, the amine compound may be added in excess to the liquid phase in comparison with the aforementioned amount (equivalent amount to the total amount of the ligand groups).

The production method of the present embodiment is not particularly limited as long as the above-mentioned complex compound having the 1 st metal atom and the complex compound having the 2 nd metal atom, and if necessary, the chalcogen compound and the amine compound are reacted in a liquid phase. The production method of the present embodiment can be performed by a known method such as a thermal injection method, a heating method, or a flow synthesis method.

The blending ratio of the complex compound having the 1 st metal atom and the complex compound having the 2 nd metal atom may be adjusted according to the composition of the chalcogen perovskite as the target.

In the production method according to one embodiment, when a material including at least a complex having a1 st metal atom, a complex having a2 nd metal atom, and a solvent is used as a raw material component, a1 st raw material including at least the solvent in the raw material component and a2 nd raw material including at least the remaining raw material component not included in the 1 st raw material in the raw material components are prepared. Then, the reaction is caused by adding the 2 nd raw material to the 1 st raw material.

In the present embodiment, it is preferable to add the 2 nd raw material to the 1 st raw material in a state where at least one of the 1 st raw material and the 2 nd raw material is preheated.

Alternatively, the reaction may be generated by adding the 2 nd raw material to the 1 st raw material and then heating the mixture.

The manufacturing method of the present embodiment will be described below by taking a case of performing the thermal injection method as an example.

First, the 1 st raw material is preheated. The heating rate is not particularly limited, and for example, heating is performed at a heating rate of 1 to 30℃per minute, typically 1 to 10℃per minute.

The temperature of the 1 st raw material after heating is not particularly limited, and may be, for example, room temperature to 450℃or 120 to 360 ℃.

Then, the 2 nd raw material is added to the 1 st raw material to produce a reaction of the complex compound having the 1 st metal atom and the complex compound having the 2 nd metal atom. The 2 nd material may be heated in advance in the same manner as the 1 st material. The rate of addition of the 2 nd raw material is not particularly limited, and is preferably adjusted in consideration of a decrease in temperature of the liquid phase caused by addition of the 2 nd raw material.

The liquid phase temperature after mixing is preferably from room temperature to 450 ℃, more preferably from 120 to 360 ℃, still more preferably from 220 to 330 ℃.

For example, in the case where either one of the complex compound having the 1 st metal atom and the complex compound having the 2 nd metal atom has the ligand (dithiocarbamate (S ₂CNR₂)) represented by the above formula (1), if the temperature of the liquid phase is 120 ℃ or higher, the reaction of the metal complex compound having the ligand can be initiated by the amine-based compound, and therefore the reaction of the complex compound having the 1 st metal atom and the complex compound having the 2 nd metal atom proceeds smoothly. In this case, the temperature of the liquid phase is preferably set to be higher than 120 ℃.

In addition, by setting the temperature of the liquid phase to 360 ℃ or lower, vaporization of a solvent which is generally used can be suppressed, and stable liquid phase synthesis can be performed.

In this embodiment, when all components (solvent, complex having the 1 st metal atom and complex having the 2 nd metal atom) contributing to the synthesis of chalcogen perovskite are provided in the liquid phase by adding the 2 nd raw material to the 1 st raw material in a state where the 1 st raw material is heated in advance, all of these components suddenly reach a high temperature state, and therefore the reaction start time of the complex having the 1 st metal atom and the reaction start time of the complex having the 2 nd metal atom can be made substantially simultaneously. Therefore, the reaction of the complex compound having the 1 st metal atom and the reaction of the complex compound having the 2 nd metal atom proceed well in balance, and the chalcogen perovskite can be synthesized with high purity.

In one embodiment, when the amine-based compound described above is added as a reaction initiator to the liquid phase, the raw material components include a solvent, a complex compound having a 1 st metal atom, a complex compound having a2 nd metal atom, and an amine-based compound. The method of combining the component as the 1 st raw material and the component as the 2 nd raw material is not particularly limited.

For example, the 1 st raw material may be used as a solvent alone, the 2 nd raw material may be used as a mixture of a complex compound having the 1 st metal atom, a complex compound having the 2 nd metal atom, and an amine compound.

The 1 st raw material may be a mixture of a solvent and an amine compound, and the 2 nd raw material may be a mixture of a complex compound having a 1 st metal atom and a complex compound having a 2 nd metal atom.

The 1 st raw material may be a mixture of a solvent and either a complex compound having a1 st metal atom or a complex compound having a 2 nd metal atom, or a mixture of an amine compound and the other of a complex compound having a1 st metal atom or a complex compound having a 2 nd metal atom.

In one embodiment, in the case where the chalcogen compound described above is added to the liquid phase, the raw material component contains a solvent, a complex compound having a1 st metal atom, a complex compound having a2 nd metal atom, and a chalcogen compound.

In this case, the method of combining the component as the 1 st raw material and the component as the 2 nd raw material is not particularly limited.

For example, the 1 st raw material may be used as a solvent alone, the 2 nd raw material may be used as a mixture of a complex compound having a1 st metal atom, a complex compound having a2 nd metal atom, and a chalcogen compound.

The 1 st raw material may be a mixture of a solvent and a chalcogen compound, and the 2 nd raw material may be a mixture of a complex compound having a1 st metal atom and a complex compound having a 2 nd metal atom.

The 1 st raw material may be a mixture of a solvent and either a complex compound having a 1 st metal atom or a complex compound having a 2 nd metal atom, or a mixture of a chalcogen compound and the other of a complex compound having a 1 st metal atom or a complex compound having a 2 nd metal atom.

In one embodiment, the liquid phase obtained by adding the 2 nd raw material to the 1 st raw material is heated and stirred for 0 to 24 hours while maintaining the temperature of preferably room temperature to 450 ℃, more preferably 120 to 360 ℃, still more preferably 220 to 330 ℃. After completion of the stirring, the precipitate precipitated in the liquid phase is separated by a known method, whereby a chalcogen perovskite as a target substance can be obtained.

The reason for the suitability of 120℃or higher and the suitability of 360℃or lower is the same as that described in the example of the case of using the thermal injection method.

In the above-described series of liquid phase synthesis, it is preferable to perform the synthesis in a state where components such as water and oxygen are removed as much as possible so that the components are not present in the synthesis atmosphere. For example, the above-described series of liquid phase syntheses are preferably carried out under an inert atmosphere filled with nitrogen and argon.

The production method of the present embodiment may be performed by, for example, a flow synthesis method described below.

First, at least 1 of the complex compound having the 1 st metal atom, the complex compound having the 2 nd metal atom, the chalcogen compound and the amine compound is dissolved in a solvent, and the solution is circulated as a raw material stream of 3 lines or 4 lines.

Then, the reaction is initiated by bringing all of the feed streams together simultaneously or stepwise. At this time, at least 1 of the raw material streams is preferably heated in advance before joining. The preheated feedstream is preferably the most fluid stream. Further, since the reaction site of the flow synthesis is small, even if the respective raw material streams are heated immediately after the joining, the temperature can be instantaneously raised, and the reaction start time of the complex having the 1 st metal atom and the reaction start time of the complex having the 2 nd metal atom can be made substantially simultaneously. The heating rate during heating and the temperature of the heated component are the same as those of the heat injection method. The following steps are similar to the thermal injection method.

According to the flow synthesis method, the temperature of the components contributing to the synthesis of the chalcogen perovskite can be raised in a short time after the joining, and therefore the reaction start time of the complex having the 1 st metal atom and the reaction start time of the complex having the 2 nd metal atom can be made substantially simultaneously. In addition, since the reaction sites for the flow synthesis are small, the collision probability of the raw materials, that is, the reaction efficiency is high. Therefore, the reaction of the complex compound having the 1 st metal atom and the reaction of the complex compound having the 2 nd metal atom proceed well in balance, and the chalcogen perovskite can be synthesized with high purity.

In addition, the yield of chalcogen perovskite is improved, and the energy cost can be reduced. In addition, since the amount of waste of impurities contained in the final composition can be reduced, the environmental load can be reduced. In addition, since accidents such as explosion on the production line caused by impurities can be prevented, the safety in production can be improved.

The production method of the present embodiment described above can obtain particles of chalcogen perovskite without performing a firing step. In general, when the firing step is performed, nano-sized primary particles are aggregated to generate secondary particles, but when the firing step is not performed, generation of such secondary particles is suppressed. Thus, it is possible to obtain nano particles of chalcopyrite having a fine crystallite size.

Since the production method of the present embodiment described above is based on the liquid phase synthesis method, impurities are less likely to be mixed into particles during the synthesis than in the solid phase synthesis method. Further, since the liquid phase synthesis method is characterized by homogeneous nucleation/particle growth from the liquid phase, fine nanoparticles having a narrow particle size distribution can be obtained by preventing agglomeration of nuclei generated in the liquid phase (for example, refer to "crab Jiang Chengzhi et al," liquid phase synthesis of' size/morphology controlling functional inorganic nanoparticles and development of a hybrid material based on precise organic modification of the surface thereof, "society for crystal growth, 2017, volume 44, phase 2, pages 66-73").

Therefore, according to the production method of the present embodiment, it is possible to obtain chalcoperovskite nanoparticles which have a small mixing of impurities in particles, a narrow and uniform particle size distribution, and a fine crystallite size.

[ Mode at the time of use ]

Examples of the manner of using the chalcoperovskite according to one embodiment of the present invention include: powder, film, sheet, etc.

(Powder)

In the present specification, the powder of chalcogen perovskite means a substance obtained by aggregation or agglomeration of chalcogen perovskite.

The powder of the chalcogen perovskite may contain other materials than the chalcogen perovskite as additives for the purpose of improving various characteristics such as light emission characteristics, dispersibility into other materials, film forming properties when used as a dispersion liquid or other compositions as described later.

In the following description, a polycrystal of the chalcogen perovskite (for example, a polycrystal denoted by symbol 20 in fig. 1), or a single crystal of the chalcogen perovskite is sometimes referred to as primary particles of the chalcogen perovskite.

In the following description, the primary particles of chalcogen perovskite are sometimes referred to as secondary particles. That is, the chalcogen perovskite powder means an aggregate of primary particles and/or secondary particles of chalcogen perovskite, or a mixture of these and an additive.

In the present specification, when the primary particles of the chalcogen perovskite are single crystals, the size d20 of the primary particles corresponds to the diameter d10 of the crystallites. In the case where the primary particles of the chalcogen perovskite are polycrystalline including crystallites having a diameter d10 (corresponding to the polycrystalline 20 in fig. 1), the size d20 of the primary particles corresponds to the diameter of the polycrystalline 20.

The sizes of the primary particles and the secondary particles of the chalcogen perovskite contained in the powder are not particularly limited. The primary particles preferably have a size of, for example, 5 to 1000nm, more preferably 5 to 100nm, and still more preferably 5 to 20nm.

Primary or secondary particles of chalcogenides may also be surface modified with ligands.

The kind of the ligand to modify the surface of the primary particle or the secondary particle is not particularly limited, and examples thereof include one or more selected from the group consisting of oleylamine, oleic acid, dodecylmercaptan and trioctylphosphine.

The use of the chalcoperovskite powder is not particularly limited. For example, the chalcogen perovskite powder may be dispersed in a liquid dispersion medium and used as the dispersion liquid, or the chalcogen perovskite powder may be dispersed in a resin or a solid medium (solid dispersion medium) and used as a composition.

The chalcogen perovskite powder may be sintered to form a sintered body for use. The sintered perovskite powder can be used as a sputtering target, for example.

The chalcogen perovskite powder may be used in a state where the powder is maintained. The chalcogen perovskite powder can be used as a vapor deposition source in vapor deposition treatment, for example.

(Film)

In the present specification, the thin film of chalcogen perovskite means a film obtained by surface-like aggregation of chalcogen perovskite.

For the purpose of improving various properties such as dispersibility of the chalcogen perovskite in the film and luminescence properties, the thin film of the chalcogen perovskite may contain other materials than the chalcogen perovskite as additives.

The sizes of the primary particles and the secondary particles of the chalcogen perovskite contained in the thin film of the chalcogen perovskite are not particularly limited. The size of the primary particles contained in the film is, for example, preferably 5 to 1000nm, more preferably 5 to 100nm, and even more preferably 5 to 20nm.

The method for producing the film is not particularly limited.

For example, a thin film of a chalcogen perovskite can be formed by using a dispersion in which nanoparticles of a chalcogen perovskite are dispersed in a liquid dispersion medium, or a precursor material of a chalcogen perovskite (for example, a dispersion in which a complex compound having a 1 st metal atom and a complex compound having a 2 nd metal atom are dispersed in a dispersion medium), forming a film by a solution film-forming method such as a coating method, a spray method, a doctor blade method, or an inkjet method, and then drying, firing, or other treatments as necessary.

For example, when a precursor material (a dispersion liquid obtained by dispersing a complex compound having a1 st metal atom and a complex compound having a2 nd metal atom in a dispersion medium) is used as a film-forming material, a film is formed by a solution film-forming method such as a coating method, and the coating film is subjected to a heat treatment at a predetermined temperature, whereby the complex compound having a1 st metal atom and the complex compound having a2 nd metal atom react in the coating film. Thus, a thin film containing chalcogen perovskite according to one embodiment of the present invention can be obtained.

The method for forming a thin film is not limited, and for example, a thin film of chalcogen perovskite may be formed by forming a film of nanoparticles of chalcogen perovskite (for example, a powder containing nanoparticles, a molded body or a fired body of the powder) or a precursor material of chalcogen perovskite by a vacuum process using a sputtering method, a vacuum vapor deposition method, or the like, and then firing or other treatments as necessary.

In the case of performing a treatment such as heating or firing, the chalcogen perovskite in the finally obtained thin film may not necessarily maintain the particle shape before the heating treatment or the like.

(Sheet material)

In the present specification, the sheet of chalcogen perovskite means a substance in which a composition in which chalcogen perovskite is dispersed in a solid dispersion medium is formed in a planar shape.

For the purpose of improving various properties such as dispersibility and luminescence properties of the chalcoperovskite, the sheet of the chalcoperovskite may contain, in addition to the chalcoperovskite, silica particles, acids, bases, binder materials, and the like as additives.

The sizes of the primary particles and the secondary particles of the chalcogen perovskite contained in the sheet of the chalcogen perovskite are not particularly limited. The size of the primary particles contained in the sheet is, for example, preferably 5 to 1000nm, more preferably 5 to 100nm, and even more preferably 5 to 20nm.

As a solid dispersion medium for the sheet of chalcogen perovskite, a known polymer material for this purpose can be arbitrarily applied.

In one embodiment, the polymer material as the solid dispersion medium for the sheet of chalcogen perovskite is suitably a material that exhibits a translucent or substantially transparent appearance when made into a sheet shape.

The solid dispersion medium used for the sheet of chalcogen perovskite is not particularly limited, and examples thereof include: polyvinyl butyral, polyvinyl acetate, silicones and silicone derivatives.

Examples of the derivative of the silicone include: polyphenylmethylsiloxanes, polyphenylalkylsiloxanes, polydiphenylsiloxanes, polydialkylsiloxanes, fluorinated silicones, vinyl-and hydride-substituted silicones.

As the solid dispersion medium for the sheet, in addition to the above, for example, an ionomer, polyethylene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polypropylene, polyester, polycarbonate, polystyrene, polyacrylonitrile, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ethylene-methacrylic acid copolymer film, nylon, or the like can be used.

The method for producing the sheet is not particularly limited.

For example, a sheet of the chalcogen perovskite may be produced by kneading and stretching the powder of the chalcogen perovskite with a solid dispersion medium.

Further, the composition can be produced by coating a liquid composition obtained by mixing a chalcogen perovskite with various additives, into a sheet form, and then drying the sheet form, if necessary.

In the above films and sheets, primary particles or secondary particles of chalcogen perovskite contained in them may be surface-modified with ligands.

The kind of the ligand is not particularly limited, and for example, the same ligands as those exemplified in the project of the powder of chalcoperovskite can be used.

[ Use ]

The use of the chalcoperovskite obtained by the production method of the present embodiment is not particularly limited. The chalcogenides according to one embodiment of the present invention are suitable, for example, as a light-emitting material, a wavelength conversion element, and a photoelectric conversion element in a light-emitting device such as a display.

The chalcogen perovskite according to one embodiment of the present invention, or the powder, dispersion, film (membrane), or sheet using the same, may be applied to Down-Conversion (Down-Conversion) of ultraviolet light, blue light, or the like in various devices.

The chalcoperovskite according to one embodiment of the present invention, or the powder, dispersion, film (membrane), sheet using the same, can be suitably used for various devices such as a light-emitting device including an LED or an organic EL, a display device including the light-emitting device, an illumination device including the light-emitting device, an image sensor, a photoelectric conversion device, and a bioluminescence mark.

These various devices may also have, for example, a film (membrane) or sheet comprising chalcogenides according to one form of the present invention.

Examples

Production example 1

(Synthesis of diisobutyldithiocarbamic acid Ba)

Barium hydroxide (5140 mg) was weighed and placed in a 100ml three-necked flask, and 50ml of pure water was added thereto and the mixture was sealed, followed by stirring.

Then, diisobutylamine (10.39 ml) was added to the three-necked flask, followed by stirring for 10 minutes, and then carbon disulfide (3.63 ml) was added thereto and stirred for 3 hours. It was confirmed that a white solid was slowly precipitated by stirring.

The precipitated solid was filtered and recovered, washed with hexane, and then vacuum-dried to obtain a composition containing diisobutyldithiocarbamic acid Ba. The yield was about 70%.

Production example 2

(Synthesis of diisobutyldithiocarbamic acid Zr)

Zirconium chloride (2913 mg) was weighed and placed in a 200ml three-necked flask, 75ml of THF was added thereto, and the vessel was sealed, followed by stirring for about 15 minutes.

Then, diisobutylamine (29.2 ml) was added to the three-necked flask, followed by stirring for 10 minutes, carbon disulfide (10.2 ml) was further added thereto, and stirring was further carried out for 3 hours.

After the completion of stirring, the precipitated solid was filtered, and the filtrate was recovered and transferred to another vessel.

Then, after the solvent was removed from the recovered filtrate by a known method, the resulting residue was dispersed in hexane to obtain a white suspension.

The white suspension was filtered, and the resulting solid was washed with hexane and then dried in vacuo to give a composition comprising diisobutyldithiocarbamic acid Zr. The yield was about 80%.

Example 1

The diisobutyldithiocarbamic acid Ba (527.94 mg) obtained in production example 1 and the diisobutyldithiocarbamic acid Zr (908.76 mg) obtained in production example 2 were weighed and placed in a 50ml three-necked flask, and 1-octadecene (5 ml) was added and stirred.

Then, the three-necked flask was moved into a ventilator while keeping the internal atmosphere at N ₂, and after the temperature was raised to 310℃at a temperature-raising rate of 5℃per minute, the normal-temperature oleylamine (1600 mg) was injected by a Luer-Lock syringe.

Then, the solution in the three-necked flask was kept at 310℃and stirred for 3 hours, and then, excess 1-butanol was introduced into the flask and quenched (quenched).

Then, the solution in the three-necked flask was collected, centrifuged, and the collected solid was redispersed in hexane and filtered to obtain a composition.

Example 2

A composition was obtained in the same manner as in example 1, except that the injection amount of oleylamine injected into the three-necked flask was changed from 1600mg to 3200 mg.

Comparative example 1

The synthesis was performed in the same manner as in example 1 of US 2019/0225883 A1.

First, a mixture of a metal precursor obtained by mixing barium acetate and zirconium acetate hydroxide in a ratio of 1:1 (molar ratio) and oleic acid were dissolved in 1-octadecene as a solvent in a 200ml reaction vessel, and heated at 90℃for 60 minutes under vacuum.

The blending amount of oleic acid was set to 10 moles per 1 mole of the mixture of metal precursors.

Then, the atmosphere in the reaction vessel was replaced with nitrogen, and the temperature in the reactor was raised to 330 ℃.

Then, after a solution (S/ODE) in which sulfur was dispersed in octadecene was injected into a reaction vessel, the mixture was reacted for 30 minutes while maintaining the temperature in the reaction vessel at 310 ℃.

The sulfur injection amount was set to about 10 moles per 1 mole of the mixture of metal precursors.

Then, the reaction mixture in the reaction vessel was quenched to room temperature, acetone was added thereto, and the resultant precipitate was dispersed in toluene after centrifugation, and the composition was recovered from the resultant dispersion.

[ X-ray diffraction analysis ]

The compositions obtained in example 1, example 2 and comparative example 1 were subjected to X-ray diffraction analysis by the following methods.

Wavelength of X-ray: (CuK alpha ray)

Measurement range: 5-60 (deg)

The measuring method comprises the following steps: 2 theta-theta process

Measuring a sample: the samples having the flat surfaces were measured by filling the glass sample holders with the sample powders of the compositions obtained in example 1, example 2 and comparative example 1.

The X-ray diffraction spectra obtained for example 1 and example 2 are shown in fig. 2.

In the X-ray diffraction spectra obtained for example 1, example 2 and comparative example 1, the peak positions showing the peak intensities from the highest peak intensity to the top 5 are shown in table 1 (example 1 and example 2) and table 2 (comparative example 1), respectively.

In addition, for BaZrS ₃(GdFeO₃ orthorhombic perovskite synthesized by solid phase synthesis; space group Pnma), the peak positions showing peak intensities from the highest peak intensity to the top 5 th peak intensity in the X-ray diffraction spectrum confirmed by JCPDS card nos. 00-015-0327 and ICSD (Inorganic Crystal Structure Database ) #23288 are shown in table 1 together with the respective lattice crystal plane indices.

In FIG. 2, the peak positions of the X-ray diffraction patterns confirmed by the above-mentioned databases (JCPDS card No.00-015-0327 and ICSD (Inorganic Crystal Structure Database) # 23288) are shown as straight lines.

As a result of the above-described X-ray diffraction, the peak of the X-ray diffraction spectrum obtained in comparative example 1 showed substantially the same peak as the X-ray diffraction spectrum (fig. 4) shown in example 1 for US2019/0225883 Al.

TABLE 1

TABLE 2

From table 1, it was confirmed that, in the compositions obtained in example 1 and example 2, the peak positions showing the top 5-position peak intensities in the X-ray diffraction analysis spectra were approximately identical to the BaZrS ₃(GdFeO₃ -type orthorhombic perovskite synthesized by solid phase synthesis based on JCPDS cards. In consideration of measurement errors and the like caused by the measurement device, the deviation of the peak position from the peak position within ±1 (deg) based on the JCPDS card is within the allowable range.

On the other hand, the peak position showing the peak intensity at the first 5 th position in the X-ray diffraction analysis spectrum was greatly different from BaZrS ₃ th position synthesized by solid phase synthesis with respect to the composition obtained in comparative example 1. That is, the following results were formed: it is presumed that components other than BaZrS ₃ are mixed in the composition or BaZrS ₃ having the structure described in JCPDS card is not synthesized as a main component.

[ Particle size based on Shelle formula ]

In the X-ray diffraction spectra obtained in examples 1 and 2 (see fig. 2), the crystallite size τ1 was calculated based on the diffraction peak 1 having the largest peak height by the scherrer formula shown in the following formula (a). The results are shown in Table 3. The half-peak width β was obtained by the following method: the peaks in the spectrum were analyzed by X-ray diffraction and the peaks were connected by straight lines, and after removing the background, they were obtained by fitting by using a Split Pseudo-Voigt function.

Τ1=k/β cOs θ … (a)

Θ: diffraction angle of maximum peak [ rad ]

Beta: half peak width of maximum peak [ rad ]

K: form factor

The method comprises the following steps: wavelength of X-ray

Τ1: crystallite size

TABLE 3

[ Particle size based on Williamsen-Hall formula ]

The crystallite size τ2 was calculated by the wilamason-Hall formula (Williamson-Hall formula) shown in the following formula (b) based on each diffraction peak of the X-ray diffraction spectra obtained in example 1 and example 2 (see fig. 2). The half-peak width γ was obtained by the following method: the peaks in the spectrum were analyzed by X-ray diffraction and the peaks were connected by straight lines, and after removing the background, they were obtained by fitting by using a Split Pseudo-Voigt function.

Beta cos θ=ε (2 sin θ) +K-d/τ2 … (b)

Θ: diffraction angle of diffraction peak [ rad ]

Beta: half-width of diffraction peak [ rad ]

K: form factor

The method comprises the following steps: wavelength of X-ray

Epsilon: lattice strain

Τ2: crystallite size

Specifically, for each diffraction peak (peak 1:25deg (0.22 rad), peak 2:45deg (0.39 rad), peak 3:52deg (0.45 rad)) observed in the X-ray diffraction spectrum shown in fig. 2, the diffraction angle θ and half-peak width γ (see table 4) were substituted into the above formula (b), and the sin θ was plotted as the X-axis and the βcos θ was plotted as the y-axis, thereby forming an approximate straight line.

An approximate straight line (y=0.0248 x+0.0101) made by plotting peak 1, peak 2 and peak 3 of example 1 is shown in fig. 3A. In addition, an approximate straight line (y=0.0188x+0.0192) made by plotting peak 1, peak 2 and peak 3 of example 2 is shown in fig. 3B.

TABLE 4

Then, lattice strain ε is calculated from each slope (2ε) of the approximate straight line, and crystallite size τ2 is calculated from the intercept (K/τ2). The results are shown in Table 5.

TABLE 5

The composition obtained in example 1 was observed at an acceleration voltage of 5kV and a magnification of 25 ten thousand times (hereinafter, referred to as SEM observation) using a scanning electron microscope (JSM-7610F, manufactured by Japanese electric Co., ltd.) at 2 sites arbitrarily selected.

Fig. 4 and 5 show images (hereinafter, referred to as SEM images) obtained by SEM observation with a scanning electron microscope of the composition obtained in example 1.

The SEM images shown in fig. 4 and 5 are images captured so as to contain 260 or more particles within the captured image. An image of one of the 2 sites observed is shown in fig. 4, and an image of the other is shown in fig. 5.

The composition obtained in example 2 was observed at an acceleration voltage of 5kV, 20 ten thousand times or 40 ten thousand times (hereinafter referred to as STEM observation) using a scanning transmission electron microscope (JSM-7610F, manufactured by Japanese electric Co., ltd.) at 2 sites arbitrarily selected.

Specifically, 1 site out of 2 sites arbitrarily selected from the composition obtained in example 2 was observed at a magnification of 20 ten thousand times, and the other site was observed at a magnification of 40 ten thousand times.

Fig. 6 (20 ten thousand times magnification) and fig. 7 (40 ten thousand times magnification) show images (hereinafter referred to as STEM images) obtained by STEM observation by a scanning transmission electron microscope of the composition obtained in example 2.

The STEM image shown in fig. 6 is an image captured so as to include 200 or more particles within the captured image. The STEM image shown in fig. 7 is an image captured so as to include 450 or more particles in the captured image range.

In each of the images shown in fig. 4 to 7, the equivalent diameter of the projected area circle of the particles that can be confirmed in the image was measured, and particles P _L that have the equivalent diameter of the projected area circle of 10 μm or more were identified among the particles that were the objects of measurement.

The total area occupied by the particles P _L existing in the image range is calculated for each image, and the ratio to the total area occupied by the particles existing in the image range is calculated by the following formula (α).

(Total area occupied by particles P _L present in the image)/(total area occupied by particles present in the image). Times.100: 100 … (. Alpha.)

In the SEM image shown in fig. 4, the value calculated by the formula (α) is 0%, and in the SEM image shown in fig. 5, the value calculated by the formula (α) is 0%.

Similarly, in the STEM image shown in fig. 6, the value calculated by the formula (α) is 0%, and in the STEM image shown in fig. 7, the value calculated by the formula (α) is 0%.

In each SEM image shown in fig. 4 and 5, the width indicated by a white line on the lower end side corresponds to 100nm.

As is clear from fig. 4 and 5, particles having a particle diameter exceeding 100nm (equivalent diameter of the projected area circle) were not confirmed in any SEM image obtained by photographing the composition of example 1.

Similarly, in the STEM image shown in fig. 6, the width indicated by the white line on the lower end side corresponds to 100nm, and in the STEM image shown in fig. 7, the width indicated by the white line on the lower end side corresponds to 10nm.

As is clear from fig. 6 and 7, no particles having a particle diameter exceeding 100nm (equivalent diameter of the projected area circle) were confirmed in any STEM image obtained by photographing the composition of example 2.

Industrial applicability

The chalcogenides of the present invention can be applied to, for example, a light-emitting material, a wavelength conversion element, and a photoelectric conversion element in a light-emitting device such as a display.

While the foregoing has described in detail some embodiments and/or examples of the present invention, those skilled in the art will readily appreciate that many modifications are possible in the exemplary embodiments and/or examples without materially departing from the novel teachings and effects of this invention. Accordingly, these various modifications are included within the scope of the present invention.

The contents of the documents described in this specification and the application underlying the paris convention based priority of the present application are all incorporated by reference.

Claims

1. A chalcogen perovskite in which, in an X-ray diffraction spectrum obtained by X-ray diffraction measurement, a crystallite size τ1 calculated by using a Shelle formula is smaller than 40nm based on a diffraction peak having a maximum peak height,

In the image range photographed by a microscope, the proportion of the total area occupied by particles having a particle diameter of 10 μm or more measured by a microscope to the total area occupied by particles existing in the photographed image range is 10% or less.

2. A chalcogen perovskite according to claim 1, wherein the crystallite size τ2 calculated using the wilhelmy-hall formula is 34.5nm or less based on an X-ray diffraction spectrum obtained by X-ray diffraction measurement.

3. A chalcopyrite according to claim 2, wherein the crystallite size τ2 is 30nm or less.

5. A chalcogen perovskite according to any one of claims 1 to 4, wherein the chalcogen perovskite has a composition represented by the following formula (101) or (102),

ABCh₃…(101)

A′₂A_n-1B_nCh_3n+1…(102)

In the formulas (101) and (102), A, A' is Sr, ba or a combination thereof, B is Zr, hf or a combination thereof, and Ch is S, se, te or a combination thereof; in formula (102), n is an integer of 1 to 10 inclusive; in formula (102), A, A' may be the same as or different from each other; the chalcogenides may be solid solutions in which part or all of A, A', B, ch are replaced with other elements in the composition represented by formula (101) or (102).

6. A chalcogen perovskite according to any one of claims 1 to 5, wherein particles of the chalcogen perovskite are surface-modified with ligands.

7. A composition having the chalcogen perovskite according to any one of claims 1 to 6 dispersed in a dispersion medium.

8. The composition according to claim 7, which is a dispersion using a liquid dispersion medium as the dispersion medium.

10. The composition according to claim 7, which is a sheet using a solid dispersion medium as the dispersion medium.

11. The composition of claim 10, wherein the solid dispersion medium is at least one selected from the group consisting of polyvinyl butyral, polyvinyl acetate, and silicone and derivatives thereof.

12. A powder comprising the chalcopyrite according to any one of claims 1 to 6.

13. The powder of claim 12, wherein the primary or secondary particles of the chalcogen perovskite are surface-modified with ligands.

14. A sintered body obtained by sintering the powder according to claim 12 or 13.

15. A film comprising a chalcopyrite according to any of claims 1 to 6.

16. The method for producing a film according to claim 15, wherein the dispersion according to claim 8 or 9 is formed into a film by a coating method, a spray method, a doctor blade method, or an inkjet method.

17. The method for producing a thin film according to claim 15, wherein the powder of the chalcogen perovskite according to claim 12 or 13 is formed into a film by a sputtering method or a vacuum evaporation method.

18. The method for producing a sheet according to claim 10, wherein the dispersion liquid according to claim 8 or 9 is dried after being coated in a sheet form.

19. A luminescent material comprising a chalcogen perovskite according to any one of claims 1 to 6.

20. A light emitting device, an image sensor, a photoelectric conversion device, or a bioluminescent label comprising the chalcogen perovskite according to any one of claims 1 to 6.

22. The production method according to claim 21, wherein the complex compound having a1 st metal atom and the complex compound having a2 nd metal atom each have a ligand coordinated by an atom selected from the group consisting of a nitrogen atom (N), a sulfur atom (S), a selenium atom (Se), a tellurium atom (Te), a carbon atom (C) and a phosphorus atom (P).

23. The production method according to claim 21 or 22, wherein the metal atom of the complex compound having a1 st metal atom is at least one of Sr and Ba,

The metal atom of the complex compound having the 2 nd metal atom is at least one of Zr and Hf.

25. The production method according to any one of claims 21 to 24, wherein the ligand is a dithiocarbamate, xanthate, trithiocarbamate, dithioester, thiolate, sulfide, or a compound in which part or all of sulfur atoms contained in them is replaced with selenium atoms or tellurium atoms, an alkylamine, arylamine, trialkylsilylamine, a nitrogen-containing aromatic ring, an alkane, an unsaturated hydrocarbon ring, or a group derived from the unsaturated hydrocarbon ring, a cyano group, a trialkylphosphine, a triarylphosphine, or a diphosphine.

ABCh₃…(101)

A′₂A_n-1B_nCh_3n+1…(102)

30. The production method according to any one of claims 21 to 29, wherein an amine compound is further added.

33. The production method according to any one of claims 21 to 32, wherein the reaction is caused by adding a 2 nd raw material to a1 st raw material containing at least a solvent, among raw material components including the complex compound having a1 st metal atom, the complex compound having a 2 nd metal atom, and the solvent, the 2 nd raw material containing at least a raw material component not contained in the 1 st raw material among the raw material components.

35. The production method according to claim 33, wherein the reaction is produced by heating the 1 st raw material and the 2 nd raw material after adding the 2 nd raw material to the 1 st raw material.

36. The production method according to claim 35, wherein the obtained coating film is heat-treated by forming a film of a dispersion in which the complex compound having the 1 st metal atom and the complex compound having the 2 nd metal atom are dispersed in a dispersion medium by a coating method, a spraying method, a doctor blade method or an ink jet method.

37. The production method according to any one of claims 21 to 32, wherein the reaction is produced by simultaneously mixing the complex compound having a 1 st metal atom, the complex compound having a 2 nd metal atom, and at least 1 of a chalcogen compound and an amine compound.

38. The production method according to claim 37, wherein the reaction is caused by causing at least 1 of the complex compound having a1 st metal atom, the complex compound having a 2 nd metal atom, and the chalcogen compound and the amine compound to flow in separate fluids, and causing the fluids to flow together at the same time.