CN110799626B - Composition, film, laminated structure, light-emitting device, display and method for producing the composition - Google Patents

Abstract

The present invention relates to a composition having a luminescent property, which contains a component (1) and a component (2). (1) The component (A) is a perovskite compound having A, B and X as constituent components, and the component (2) is an addition polymerizable compound having an ionic group or a polymer thereof; a is a component located at each vertex of a hexahedron centered on B in the perovskite crystal structure and is a cation having a valence of 1, X is a component located at each vertex of an octahedron centered on B in the perovskite crystal structure and is at least 1 anion selected from a halide ion and a thiocyanate ion, and B is a component located at the center of the hexahedron centered on A and the octahedron centered on X in the perovskite crystal structure and is a metal ion.

Description

Manufacture of composition, film, laminated structure, light-emitting device, display and composition method

technical field

The present invention relates to a composition, a film, a laminated structure, a light-emitting device, a display, and a method for producing the composition.

This application claims priority based on Japanese Patent Application No. 2017-123597 filed in Japan on June 23, 2017, the contents of which are incorporated herein.

Background technique

An LED backlight with a blue LED and a composition including two compounds having different emission wavelengths has been developed. In recent years, interest in perovskite compounds has been increasing as light-emitting compounds contained in the above-mentioned compositions.

For example, as a composition containing a perovskite compound, a composition in which two layers each containing a different perovskite compound are laminated has been reported (Non-Patent Document 1).

prior art literature

non-patent literature

Non-Patent Document 1: Xiaoming Li, Ye Wu, Shengli Zhang, Bo Cai, Yu Gu, JizhongSong, Haibo Zeng, Adv. Funct. Mater., 26, 2435-2445 (2016)

Contents of the invention

The technical problem to be solved in the present invention

However, the laminated composition described in the above-mentioned Non-Patent Document 1 requires a process for forming a plurality of layers, and thus cannot be said to be sufficiently productive.

Therefore, the present inventors have thought that if a single layer is formed by using a composition mixed with a plurality of perovskite compounds to obtain lights of different emission wavelengths, the number of steps can be reduced, productivity can be improved, and a compound having different emission wavelengths can be produced. Composition of 2 perovskite compounds.

In this study, the following new problem was faced: the emission wavelength of the obtained composition was measured, and as a result, the intrinsic emission wavelength of each perovskite compound disappeared, and the emission wavelength that was unique to each perovskite compound was emitted. Light of a new emission wavelength with a different wavelength.

The present invention has been made in view of the above-mentioned problems, and an object of the present invention is to provide a composition capable of maintaining a unique light emission wavelength of each perovskite compound even if a plurality of perovskite compounds having different light emission wavelengths are mixed, a production method thereof, and a use thereof. Films, laminate structures, light-emitting devices and displays of the composition.

In order to solve the above problems, the object of the present invention is to provide a steering device for a vehicle, which includes:

In order to solve the above-mentioned problems, the inventors of the present invention conducted intensive studies, and as a result, found that by using a composition containing a perovskite compound and an addition polymerizable compound having an ionic group or a polymer thereof, when mixing various perovskite compounds, In the composition composed of mineral compounds, the inherent emission wavelength of each perovskite compound can be maintained.

That is, the embodiments of the present invention include the inventions of the following [1] to [15].

[1] A composition having luminescence comprising the following (1) component and the following (2) component.

(1) Composition: Perovskite compound composed of A, B and X

(A is a component located at each apex of a hexahedron centered on B in the perovskite crystal structure, and is a monovalent cation.

X represents a component located at each apex of an octahedron centered on B in the perovskite crystal structure, and is at least one anion selected from halide ions and thiocyanate ions.

B is a component located at the center of a hexahedron with A at its apex and an octahedron with X at its apex in the perovskite crystal structure, and is a metal ion. )

(2) Component: Addition polymerizable compound or its polymer having an ionic group

[2] The composition according to [1], wherein the component (2) is a radically polymerizable compound or an ionically polymerizable compound, or a polymer thereof.

[3] The composition according to [1], wherein the addition polymerizable compound having an ionic group is selected from acrylates having an ionic group and their derivatives, At least one of methacrylates and derivatives thereof, and styrenes with ionic groups and derivatives thereof.

[4] The composition according to any one of [1] to [3], wherein the component (2) is a polymer of an addition polymerizable compound having an ionic group, and the component (1) Agglomerates are formed with the (2) component.

[5] The composition according to any one of [1] to [4], further comprising at least one selected from the following (3) component and the following (4) component.

(3) Composition: solvent

(4) Ingredients: polymeric compound or its polymer

[6] The composition according to any one of [1] to [4], which further contains the following (4') component, the total content of (1) component, (2) component and (4') component The ratio is 90% by mass or more relative to the total mass of the composition.

(4') Composition: Polymer

[7] The composition according to any one of [1] to [6], further comprising the following component (5).

(5) Component: at least one selected from ammonia, amines, carboxylic acids, and their salts or ions

[8] The composition according to any one of [1] to [7], further comprising the following component (6).

(6) Component: one or more compounds selected from the group consisting of an organic compound having an amino group, an alkoxy group, and a silicon atom, and silazane or a modified product thereof

[9] The composition according to [8], wherein the component (6) is polysilazane or a modified product thereof.

[10] The composition according to any one of [1] to [9], further comprising the following component (1)-1.

(1)-1 component: a perovskite compound having a light emission peak wavelength different from that of the above component (1)

[11] A film using the composition according to any one of [1] to [10].

[12] A laminated structure comprising the film according to [11].

[13] A light-emitting device comprising the laminated structure described in [12].

[14] A display comprising the laminated structure described in [12].

[15] A method for producing a composition, comprising: dispersing the following component (1) in the following component (3) to obtain a dispersion; mixing the obtained dispersion with the following (2' ) components are mixed to obtain a mixed solution; the obtained mixed solution is subjected to polymerization treatment to obtain a mixed solution containing a polymer of an addition polymerizable compound having an ionic group; the obtained mixed solution containing an ionic group The process of mixing the liquid mixture of the polymer of the addition polymerizable compound and the following (4) component.

(1) Composition: Perovskite compound composed of A, B and X

(A is a component located at each apex of a hexahedron centered on B in the perovskite crystal structure, and is a monovalent cation.

X represents a component located at each apex of an octahedron centered on B in the perovskite crystal structure, and is at least one anion selected from halide ions and thiocyanate ions.

B is a component located at the center of a hexahedron with A at its apex and an octahedron with X at its apex in the perovskite crystal structure, and is a metal ion. )

(2') Component: Addition polymerizable compound having an ionic group

(3) Composition: solvent

(4) Ingredients: polymeric compound or its polymer

[16] The method for producing the composition according to [15], further comprising a step of mixing the following component (1)-1 with the obtained liquid mixture containing the component (4).

(1)-1 component: a perovskite compound having a light emission peak wavelength different from that of the above component (1)

[17] The method for producing the composition according to [15], wherein the mixture of the polymer mixture containing the addition polymerizable compound having an ionic group and the component (4) is mixed. After the above step, there is also a step of mixing the above-mentioned (1)-1 component.

The effect of the invention

According to the present invention, even if a plurality of perovskite compounds having different emission wavelengths are mixed, a composition capable of maintaining the intrinsic emission wavelength of each perovskite compound, a method for producing the same, and a film and laminate using the composition can be provided Structures, light emitting devices and displays.

Description of drawings

FIG. 1 is a cross-sectional view showing an embodiment of the laminated structure of the present invention.

Fig. 2 is a cross-sectional view showing an embodiment of the display of the present invention.

FIG. 3 is a graph showing measurement results of emission spectra of compositions of Examples 2, 4 and 7. FIG.

4 is a graph showing the measurement results of the emission spectra of the compositions of Examples 9, 12 and 13.

FIG. 5 is a graph showing measurement results of emission spectra of compositions of Examples 14 and 18. FIG.

FIG. 6 is a graph showing measurement results of emission spectra of compositions of Comparative Examples 1, 2, and 3. FIG.

Detailed ways

<composition>

The composition of this embodiment has luminescence. "Luminescence of a composition" refers to the property of a composition to emit light. The composition preferably has a property of emitting light by absorbing excitation energy, and more preferably has a property of emitting light upon excitation of excitation light. The wavelength of the excitation light may be, for example, from 200 nm to 800 nm, from 250 nm to 750 nm, or from 300 nm to 700 nm.

The composition of this embodiment contains following (1) component and following (2) component.

(1) A perovskite compound comprising A, B, and X as constituents. Hereinafter, it describes as "(1) component".

A is a component located at each apex of a hexahedron centering on B in the perovskite crystal structure, and is a monovalent cation.

X represents a component located at each apex of an octahedron centered on B in the perovskite crystal structure, and is at least one anion selected from halide ions and thiocyanate ions.

B is a component located at the center of a hexahedron with A at its apex and an octahedron with X at its apex in the perovskite crystal structure, and is a metal ion.

(2) Component: an addition polymerizable compound having an ionic group or a polymer thereof. Hereinafter, it describes as "(2) component".

It is presumed that the composition of the present embodiment forms a protected region near the perovskite compound by containing the component (2). Thus, when a perovskite compound having a different emission peak wavelength from the component (1) is mixed, it is possible to suppress the disappearance of the inherent emission wavelength of each perovskite compound and the combination with each perovskite compound. Generation of light having a new emission wavelength different from the inherent emission wavelength. Therefore, it is considered that the intrinsic emission wavelength of each perovskite compound can be maintained.

In the composition of this embodiment, (1) component and (2) component may form an aggregate. When the component (1) and the component (2) form an aggregate, the component (2) is preferably a polymer of an addition polymerizable compound having an ionic group.

As long as the effects of the present invention can be obtained, the form of aggregates containing (1) component and (2) component is not limited. In this embodiment, for example, an aggregate containing (1) component and (2) component may be formed by association of (1) component covered with (2) component. In addition, in this embodiment, for example, (1) components associate with each other to form an aggregate, and (2) component covers the surface of the aggregate, thereby forming an aggregate containing (1) component and (2) component.

That is, it can be considered that by forming a protective region composed of (2) component on the surface of the aggregate,

The contact between the component (1) and the component (1) described later and the component (1)-1 of the perovskite compound having a different emission peak wavelength is suppressed, and the effect of the present invention can be obtained.

In the composition of this embodiment, as a method of observing aggregates containing (1) component and (2) component, for example, observation combinations using a scanning electron microscope (SEM) or a transmission electron microscope (TEM) can be mentioned. way of things. Furthermore, detailed element distribution can be analyzed by energy dispersive X-ray analysis (EDX measurement) using SEM or TEM.

For example, by EDX measurement using SEM or TEM, the interface between particles containing elements derived from component (1) is blocked by a region containing elements derived from (2), thereby confirming the presence of components (1) and (2) Formation of agglomerates of components.

The shape of the aggregate is not particularly limited. In addition, as long as the effect of the present invention is obtained, the average size of the aggregates is not particularly limited, and the average Feret diameter of the aggregates is preferably from 0.01 μm to 100 μm, more preferably from 0.02 μm to 20 μm, and still more preferably from 0.05 μm to 2 μm. the following.

In this specification, "Feret's diameter" refers to the maximum distance between two parallel straight lines sandwiching an observation object (aggregate) on a TEM or SEM image. As a method of calculating the average Feret diameter of aggregates, for example, a method of observing 20 or more aggregates using SEM or TEM and taking the average value thereof is mentioned. More specifically, for example, by observing 20 aggregates using SEM or TEM and taking the average value, the average Feret diameter of the aggregates can be obtained.

When the average Feret diameter of the aggregate is equal to or greater than the above-mentioned lower limit, a guard region is formed near the component (1), and when multiple perovskite compounds having different emission peak wavelengths from the component (1) are mixed, it is possible to It further suppresses the disappearance of the intrinsic emission wavelength of each perovskite compound and the generation of a new emission wavelength different from the intrinsic emission wavelength of each perovskite compound. Thereby, it is possible to further maintain the light emission wavelength specific to each perovskite compound. Moreover, when the average Feret diameter of an aggregate is below the said upper limit, the dispersibility in a solvent or resin improves. In the present embodiment, "a plurality of perovskite compounds" refers to two or more perovskite compounds, preferably two perovskite compounds. When two types of perovskite compounds are contained, it is preferable to contain component (1) and component (1)-1, a perovskite compound having a different emission peak wavelength from component (1).

That is, the composition of this embodiment may contain (1)-1 component further.

(1)-1 component: a perovskite compound having a light emission peak wavelength different from that of the above-mentioned component (1).

Furthermore, in the composition of embodiment containing (1)-1 component, (1)-1 component and (2) component may form an aggregate. (1)-Component (2) contained in the aggregate of components (1) and (2) may be the same as or different from (2) contained in the aggregate of components (1) and (2).

Even if the aggregate of (1) component and (2) component is associated with the aggregate of (1)-1 component and (2) component to form (1) component, (2) component and (1)-1 component In the case of aggregates, if there is a protected area generated by (2) component at the interface between (1) component and (1)-1 component, and the contact between (1) component and (1)-1 component is suppressed, it is considered possible Obtain the effect of the present invention.

In addition, from the viewpoint of maintaining visible light transmittance, the average Feret diameter of the aggregates of (1)-1 component and (2) component is preferably 20 μm or less. As a method of calculating the average Feret diameter of the aggregate of (1)-1 component and (2) component, the method of calculating the average Feret diameter of the aggregate of the above-mentioned (1) component and (2) component can be mentioned .

It is preferable that the composition of this embodiment further contains at least 1 sort(s) chosen from the group which consists of following (3) component and following (4) component.

(3) Ingredients: solvent. Hereinafter, it describes as "(3) component".

(4) Component: polymerizable compound or polymer thereof. However, the substances contained in the above-mentioned (2) component are excluded. Hereinafter, it describes as "(4) component".

In the composition of this embodiment, (1) component is preferably dispersed in at least one component selected from (3) component and (4) component.

The composition of this embodiment may contain the following (5) component further.

(5) Component: at least one compound or ion selected from ammonia, amine, carboxylic acid, and their salts or ions. Hereinafter, it describes as "(5) component".

The composition of this embodiment may contain the following (6) component further.

(6) Component: one or more compounds selected from organic compounds having an amino group, an alkoxy group, and a silicon atom, and silazane or a modified product thereof.

In this specification, a "modified body of silazane" refers to a compound produced by modifying silazane. The modification treatment method will be described later.

The composition of this embodiment may have other components other than said (1) component - (6) component.

Examples of other components include some impurities, compounds having an amorphous structure composed of elements constituting the perovskite compound, and polymerization initiators.

The content of other components is preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 1% by mass or less, based on the total mass of the composition.

The composition of this embodiment preferably contains the following (4') component in addition to (1) component and (2) component, and the total content ratio of (1) component, (2) component and (4') component is relative to The total mass of the above composition is 90% by mass or more.

(4') Composition: polymer.

In the composition of the present embodiment, component (1) is preferably dispersed in component (4').

In the composition of this embodiment, the total content ratio of (1) component, (2) component, and (4') component may be 95 mass % or more with respect to the total mass of the said composition, and may be 99 mass % or more , can also be 100% by mass.

The composition of the present embodiment may contain any one or both of the above-mentioned (5) component and the above-mentioned (6) component. Examples of components other than the (1) component, (2) component, (4') component, (5) component, and (6) component include the same components as the above-mentioned other components.

In the composition of the embodiment which is composed of (1) component and (2) component as an essential component, and further contains at least one selected from (3) component and (4) component, the (1) component relative to the composition The content ratio of the total mass is not particularly limited as long as the effect of the present invention is obtained. In the composition of the present embodiment, from the viewpoint of making it difficult to aggregate the perovskite compound and the viewpoint of preventing concentration quenching, the upper limit and lower limit of the content ratio of the component (1) are relative to the total mass of the composition. The value is preferably in the following range.

Specifically, the upper limit is preferably 50% by mass or less, more preferably 1% by mass or less, and even more preferably 0.5% by mass or less. In addition, from the viewpoint of obtaining a good quantum yield, the lower limit value is preferably 0.0001% by mass or more, more preferably 0.0005% by mass or more, and even more preferably 0.001% by mass or more.

The above upper limit and lower limit can be combined arbitrarily.

(1) The content rate of a component with respect to the total mass of a composition is normally 0.0001 mass % or more and 50 mass % or less.

(1) The content ratio of the component to the total mass of the composition is preferably from 0.0001% by mass to 1% by mass, more preferably from 0.0005% by mass to 1% by mass, even more preferably from 0.001% by mass to 0.5% by mass.

In the composition of the present embodiment, a composition in which the content ratio of the component (1) to the total mass of the composition is within the above-mentioned range is preferable from the viewpoint of less aggregation of the component (1) and high luminescence. of.

In the composition of the embodiment which is composed of (1) component and (2) component as an essential component, and further contains at least one selected from (3) component and (4) component, the (2) component relative to the composition The content ratio of the total mass is not particularly limited as long as the effect of the present invention is obtained. In the composition of the present embodiment, from the viewpoint of stably dispersing component (1) in component (3) and component (4), the upper limit of the content ratio of component (2) to the total mass of the composition is and the lower limit value are preferably in the following ranges.

Specifically, the above upper limit is preferably 50% by mass or less, more preferably 30% by mass or less, even more preferably 10% by mass or less. In addition, from the viewpoint of maintaining the intrinsic emission wavelength of each perovskite compound in a composition obtained by mixing a plurality of perovskite compounds, the lower limit value is preferably 0.001% by mass or more, and more preferably 0.01% by mass. % by mass or more, more preferably 0.1% by mass or more.

The above upper limit and lower limit can be combined arbitrarily.

(2) The content rate of a component with respect to the total mass of a composition is 0.001 mass % or more and 50 mass % or less normally.

(2) The content ratio of the component to the total mass of the composition is preferably from 0.01% by mass to 30% by mass, more preferably from 0.1% by mass to 10% by mass, still more preferably from 0.3% by mass to 5% by mass.

In the composition of the present embodiment, the composition in which the content ratio of the (2) component to the total mass of the composition is within the above-mentioned range enables the (1) component to be stably dispersed in the (3) component and (4) component. From the standpoint of the present invention, a composition in which a plurality of perovskite compounds are mixed is preferable from the viewpoint of being able to maintain the inherent emission wavelength of each perovskite compound.

In the composition of the embodiment which contains (1) component and (2) component as essential components, and further contains at least one selected from (3) component and (4) component, (1) component and (2) component The total content ratio with respect to the total mass of a composition will not be specifically limited as long as it has the effect of this invention.

In this embodiment, from the viewpoint of making it difficult to aggregate the perovskite compound and the viewpoint of preventing concentration quenching, the total content ratio of (1) component and (2) component is preferably as follows with respect to the total mass of the composition: scope.

Specifically, the above upper limit is preferably 60% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, particularly preferably 20% by mass or less. In addition, from the viewpoint of obtaining a good quantum yield, the lower limit value is preferably 0.0002% by mass or more, more preferably 0.002% by mass or more, and still more preferably 0.005% by mass or more.

The above upper limit and lower limit can be combined arbitrarily.

The total content ratio of (1) component and (2) component is usually 0.0002 mass % or more and 60 mass % or less with respect to the total mass of a composition.

The total content ratio of the (1) component and (2) component to the total mass of the composition is preferably 0.001% by mass to 40% by mass, more preferably 0.002% by mass to 30% by mass, still more preferably 0.005% by mass to 20% by mass. Mass% or less.

In the composition of the present embodiment, a composition in which the total content ratio of (1) component and (2) component is within the above-mentioned range with respect to the total mass of the composition is less likely to cause aggregation of (1) component and luminescence. It is also preferable from the viewpoint of performing well.

Containing (1) component, (2) component and (4') component as essential components, the total content ratio of (1) component, (2) component and (4') component is 90% with respect to the total mass of the above composition In the composition of the embodiment having mass % or more, the content ratio of the (1) component to the total mass of the composition is not particularly limited as long as it has the effect of the present invention. In this embodiment, from the viewpoint of making it difficult to aggregate the component (1) and preventing concentration quenching, the content ratio of the component (1) to the total mass of the composition is preferably 50% by mass or less, more preferably 1% by mass. mass % or less, more preferably 0.5 mass % or less.

In addition, from the viewpoint of obtaining good luminous intensity, the content ratio of the (1) component to the total mass of the composition is preferably 0.0001% by mass or more, more preferably 0.0005% by mass or more, and still more preferably 0.001% by mass or more.

The above upper limit and lower limit can be combined arbitrarily.

(1) The content rate of a component with respect to the total mass of a composition is 0.0001 mass % or more and 50 mass % or less normally.

(1) It is preferable that the content ratio of a component with respect to the total mass of a composition is 0.0001 mass % or more and 1 mass % or less. More preferably, it is 0.0005 mass % or more and 1 mass % or less, More preferably, it is 0.001 mass % or more and 0.5 mass % or less.

Among the compositions of the present embodiment, a composition in which the content ratio of the (1) component to the total mass of the composition is within the above-mentioned range is preferable in order to exhibit good luminescence.

Containing (1) component, (2) component and (4') component as essential components, the total content ratio of (1) component, (2) component and (4') component is 90% with respect to the total mass of the above composition In the composition of the embodiment having mass % or more, the content ratio of the (2) component to the total mass of the composition is not particularly limited as long as it has the effect of the present invention. In this embodiment, from the viewpoint of stably dispersing component (1) in component (4′), the content ratio of component (2) to the total mass of the composition is preferably 50% by mass or less, more preferably 10% by mass. mass % or less, more preferably 5 mass % or less.

In addition, in a composition obtained by mixing a plurality of perovskite compounds, from the viewpoint of being able to maintain the intrinsic emission wavelength of each perovskite compound, the content ratio of the (2) component to the total mass of the composition is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, still more preferably 0.1% by mass or more.

The above upper limit and lower limit can be combined arbitrarily.

(2) The content rate of a component with respect to the total mass of a composition is 0.001 mass % or more and 50 mass % or less normally.

(2) The content ratio of the component to the total mass of the composition is preferably from 0.01% by mass to 30% by mass, more preferably from 0.1% by mass to 10% by mass, still more preferably from 0.3% by mass to 5% by mass.

In the composition of this embodiment, the composition whose content ratio of (2) component with respect to the total mass of a composition falls within the said range, from the viewpoint of stably dispersing (1) component in (4') component and in A composition in which a plurality of perovskite compounds are mixed is preferable from the viewpoint of being able to maintain the inherent emission wavelength of each perovskite compound.

Containing (1) component, (2) component and (4') component as essential components, the total content ratio of (1) component, (2) component and (4') component is 90% with respect to the total mass of the above composition In the composition of embodiment with mass % or more, the total content rate of (1) component and (2) component is not specifically limited with respect to the gross mass of a composition. In this embodiment, from the viewpoint of making it difficult to aggregate the component (1) and preventing concentration quenching, the total content ratio of the component (1) and the component (2) is preferably 60% by mass relative to the total mass of the composition. % or less, more preferably 40 mass % or less, still more preferably 30 mass % or less, particularly preferably 20 mass % or less. In addition, from the viewpoint of obtaining a good quantum yield, it is preferably at least 0.0002% by mass, more preferably at least 0.002% by mass, and still more preferably at least 0.005% by mass.

The above upper limit and lower limit can be combined arbitrarily.

The total content ratio of (1) component and (2) component is usually 0.0002 mass % or more and 60 mass % or less with respect to the total mass of a composition.

The total content ratio of the (1) component and (2) component to the total mass of the composition is preferably 0.001% by mass to 40% by mass, more preferably 0.002% by mass to 30% by mass, still more preferably 0.005% by mass to 20% by mass. Mass% or less.

Among the compositions of the present embodiment, a composition in which the total content ratio of the (1) component and (2) component to the total mass of the composition is within the above range is preferable from the viewpoint of exhibiting good luminescence.

Hereinafter, the composition in this invention is demonstrated as embodiment.

<<(1) Ingredients>>

(1) The component is a compound having a perovskite crystal structure composed of A, B, and X. Hereinafter, it is described as "perovskite compound". Hereinafter, (1) component is demonstrated.

The perovskite compound contained in the composition of the present embodiment is a perovskite compound composed of A, B, and X.

A is a component located at each apex of a hexahedron centering on B in the perovskite crystal structure, and is a monovalent cation.

X represents a component located at each apex of an octahedron centered on B in the perovskite crystal structure, and is at least one anion selected from halide ions and thiocyanate ions.

B is a component located at the center of a hexahedron with A at its apex and an octahedron with X at its apex in the perovskite crystal structure, and is a metal ion.

The perovskite compound having A, B, and X as constituents is not particularly limited as long as it has the effect of the present invention, and may be a compound having any of a three-dimensional structure, a two-dimensional structure, and a quasi-two-dimensional structure .

In the case of a three-dimensional structure, the compositional formula of the perovskite compound is represented by ABX _(3+δ) .

In the case of a two-dimensional structure, the composition formula of the perovskite compound is represented by A ₂ BX _(4+δ) .

Here, δ is a number that can be appropriately changed according to the charge balance of B, and is -0.7 or more and 0.7 or less.

The perovskite compound is preferably a perovskite compound represented by the following general formula (1).

ABX _(3+δ) (-0.7≦δ≦0.7)…(1)

A is a component located at each apex of a hexahedron centering on B in the perovskite crystal structure, and is a monovalent cation.

X represents a component located at each apex of an octahedron centering on B in the perovskite crystal structure, and is one or more anions selected from halide ions and thiocyanate ions.

B is a component located at the center of a hexahedron with A at its apex and an octahedron with X at its apex in the perovskite crystal structure, and is a metal ion.

[A]

In the perovskite compound, A is a component located at each apex of a hexahedron centering on B in the above perovskite crystal structure, and is a monovalent cation.

Examples of monovalent cations include cesium ions, organic ammonium ions, or amidinium ions. In the perovskite compound, when A is a cesium ion, an organic ammonium ion with 3 or less carbon atoms, or an amidinium ion with 3 or less carbon atoms, the general perovskite compound has a formula represented by ABX _(3+δ). three-dimensional structure.

A in the perovskite compound is preferably cesium ion or organic ammonium ion.

Specific examples of the organic ammonium ion of A include cations represented by the following general formula (A3).

[chemical 1]

In the general formula (A3), R ⁶ to R ⁹ each independently represent a hydrogen atom, an alkyl group which may have an amino group as a substituent, or a cycloalkyl group which may have an amino group as a substituent. However, R ⁶ to R ⁹ do not simultaneously become hydrogen atoms.

The alkyl groups represented by R ⁶ to R ⁹ may each independently be linear or branched, and may have an amino group as a substituent.

When R ⁶ to R ⁹ are alkyl groups, the number of carbon atoms is usually 1 to 20, preferably 1 to 4, more preferably 1 to 3, and still more preferably 1, independently.

The cycloalkyl groups represented by R ⁶ to R ⁹ may each independently have an alkyl group or an amino group as a substituent.

The cycloalkyl groups represented by R ⁶ to R ⁹ each independently have usually 3-30 carbon atoms, preferably 3-11, and more preferably 3-8. The number of carbon atoms also includes the number of carbon atoms of the substituent.

The groups represented by R ⁶ to R ⁹ are preferably each independently a hydrogen atom or an alkyl group.

By reducing the number of alkyl and cycloalkyl groups contained in the general formula (A3), and by reducing the number of carbon atoms in the alkyl and cycloalkyl groups, a perovskite crystal structure with a three-dimensional structure with high luminous intensity can be obtained. compound.

When the number of carbon atoms in the alkyl group or cycloalkyl group is 4 or more, a compound partially or completely having a two-dimensional and/or quasi-two-dimensional (quasi-2D) perovskite crystal structure can be obtained. If the two-dimensional perovskite crystal structure is stacked infinitely, it is equivalent to the three-dimensional perovskite crystal structure (reference: P.P. Boix et al., J. Phys. Chem. Lett. 2015, 6, 898-907, etc.).

^The total number of carbon atoms contained in the alkyl group represented by R ⁶ to R 9 is preferably 1 to 4, and the total number of carbon atoms contained in the cycloalkyl group represented by R ⁶ to R ⁹ is preferably 3 to 4 . More preferably, one of R ⁶ to R ⁹ is an alkyl group having 1 to 3 carbon atoms, and three of R ⁶ to R ⁹ are hydrogen atoms.

Examples of the alkyl group for R ⁶ to R ⁹ include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl , neopentyl, tert-pentyl, 1-methylbutyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, 2,2-dimethylbutyl, 2,3-dimethyl Butyl, n-heptyl, 2-methylhexyl, 3-methylhexyl, 2,2-dimethylpentyl, 2,3-dimethylpentyl, 2,4-dimethylpentyl, 3 , 3-dimethylpentyl, 3-ethylpentyl, 2,2,3-trimethylbutyl, n-octyl, isooctyl, 2-ethylhexyl, nonyl, decyl, undecyl Alkyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl.

Examples of the cycloalkyl group of R ⁶ to R ⁹ each independently include a cycloalkyl group in which an alkyl group having 3 or more carbon atoms as exemplified among the alkyl groups of R ⁶ to R ⁹ forms a ring. Propyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, norbornyl, isobornyl, 1-adamantyl, 2-adamantyl, Tricyclodecyl, etc.

As the organic ammonium ion represented by A, CH ₃ NH ₃ ⁺ (also called methyl ammonium ion.), C ₂ H ₅ NH ₃ ⁺ (also called ethyl ammonium ion.) or C ₃ H ₇ NH ₃ ⁺ (also called propylammonium ion.), more preferably CH ₃ NH ₃ ⁺ or C ₂ H ₅ NH ₃ ⁺ , further preferably CH ₃ NH ₃ ⁺ .

Examples of the amidinium ion represented by A include amidinium ions represented by the following general formula (A4).

(R ¹⁰ R ¹¹ N=CH-NR ¹² R ¹³ ) ⁺ ···(A4)

In the general formula (A4), R ¹⁰ to R ¹³ each independently represent a hydrogen atom, an alkyl group which may have an amino group as a substituent, or a cycloalkyl group which may have an amino group as a substituent.

The alkyl groups represented by R ¹⁰ to R ¹³ may each independently be linear or branched, and may have an amino group as a substituent.

The number of carbon atoms in the alkyl group represented by R ¹⁰ to R ¹³ is usually 1-20, preferably 1-4, and more preferably 1-3 independently.

The cycloalkyl groups represented by R ¹⁰ to R ¹³ may each independently have an alkyl group as a substituent or an amino group as a substituent.

The cycloalkyl groups represented by R ¹⁰ to R ¹³ each independently have usually 3-30 carbon atoms, preferably 3-11, more preferably 3-8. The number of carbon atoms includes the number of carbon atoms of the substituent.

Specific examples of the alkyl groups for R ¹⁰ to R ¹³ include the alkyl groups exemplified for R ⁶ to R ⁹ each independently.

Specific examples of the cycloalkyl group for R ¹⁰ to R ¹³ include cycloalkyl groups exemplified for R ⁶ to R ⁹ each independently.

The groups represented by R ¹⁰ to R ¹³ are each independently preferably a hydrogen atom or an alkyl group.

By reducing the number of alkyl groups and cycloalkyl groups contained in the general formula (A4), and by reducing the number of carbon atoms in the alkyl groups and cycloalkyl groups, a three-dimensional perovskite compound with high luminous intensity can be obtained.

When the number of carbon atoms in the alkyl group or cycloalkyl group is 4 or more, a compound partially or completely having a two-dimensional and/or quasi-two-dimensional (quasi-2D) perovskite crystal structure can be obtained. In addition, ^{the total number of carbon atoms contained in the alkyl group represented by R 10 to R 13 is preferably 1 to 4, and the total number of carbon atoms contained in the cycloalkyl group represented by R 10 to R 13} is preferably 3 to 4. More preferably, R ¹⁰ is an alkyl group having 1 to 3 carbon atoms, and R ¹¹ to R ¹³ are hydrogen atoms.

[B]

In the perovskite compound, B is a component located at the center of a hexahedron with A at its apex and an octahedron with X at its apex in the perovskite type crystal structure, and is a metal ion. The metal ion of the B component may be a metal ion composed of one or more types selected from monovalent metal ions, divalent metal ions, and trivalent metal ions. B preferably contains divalent metal ions, and more preferably contains one or more metal ions selected from lead and tin.

[X]

In the perovskite compound, X represents a component located at each apex of an octahedron centered on B in the above perovskite crystal structure, and represents at least one anion selected from halide ions and thiocyanate ions. X may be at least one anion selected from the group consisting of chloride ion, bromide ion, fluoride ion, iodide ion and thiocyanate ion.

X can be appropriately selected according to the desired emission wavelength. For example, X can contain bromide ions.

When X is two or more halide ions, the content ratio of the above-mentioned halide ions can be appropriately selected according to the emission wavelength, for example, a combination of bromide ions and chloride ions, or bromide ions and iodide ions can be used. The combination.

When the perovskite compound has a three-dimensional structure, it has a three-dimensional network with B as the center and X as the vertex, and the vertices represented by BX ₆ share octahedrons.

In the case of a perovskite compound having a two-dimensional structure, the octahedron represented by BX ₆ with B as the center and X as the vertex shares four vertices X of the same plane, thereby forming a BX ₆ connected by two dimensions A structure in which layers consisting of A and layers consisting of A are alternately laminated.

B is a metal cation that preferably coordinates octahedrally with respect to X.

In this specification, the perovskite structure can be confirmed by X-ray diffraction patterns.

In the case of a compound having a perovskite crystal structure of the above-mentioned three-dimensional structure, in the X-ray diffraction pattern, a peak derived from (hkl)=(001) is usually confirmed at a position of 2θ=12 to 18°, or at A peak derived from (hkl)=(110) was confirmed at the position of 2θ=18 to 25°. More preferably, a peak derived from (hkl)=(001) is confirmed at a position of 2θ=13 to 16°, or a peak derived from (hkl)=(110) is confirmed at a position of 2θ=20 to 23°.

In the case of a compound having a perovskite-type crystal structure having the above-mentioned two-dimensional structure, it is more preferable that in the X-ray diffraction pattern, the formula derived from (hkl)=(002) is generally confirmed at a position of 2θ=1 to 10°. As for the peak, the peak derived from (hkl)=(002) was confirmed at the position of 2θ=2 to 8°.

As a perovskite compound, a compound having a three-dimensional perovskite-type crystal structure represented by ABX _(3+δ) Specific examples preferably include CH ₃ NH ₃ PbBr ₃ , CH ₃ NH ₃ PbCl ₃ , CH ₃ NH ₃ PbI ₃ , CH ₃ NH ₃ PbBr _(3-y) I _y (0<y<3), CH ₃ NH ₃ PbBr _(3-y) Cl _y (0<y<3), (H ₂ N=CH -NH ₂ )PbBr ₃ , (H ₂ N=CH-NH ₂ )PbCl ₃ , (H ₂ N=CH-NH ₂ )PbI ₃ ,

CH ₃ NH ₃ Pb _(1-a) Ca _a Br ₃ (0<a≦0.7), CH ₃ NH ₃ Pb _(1-a) Sr _a Br ₃ (0<a≦0.7), CH ₃ NH ₃ Pb _{( 1-a)} La _a Br _(3+δ) (0<a≦0.7,0<δ≦0.7), CH ₃ NH ₃ Pb _(1-a) Ba _a Br ₃ (0<a≦0.7), CH ₃ NH ₃ Pb _(1-a) Dy _a Br _(3+δ) (0<a≦0.7,0<δ≦0.7),

CH ₃ NH ₃ Pb _(1-a) Na _a Br _(3+δ) (0<a≦0.7,-0.7≦δ<0), CH ₃ NH ₃ Pb _(1-a) Li _a Br _{(3+δ )} (0<a≦0.7,-0.7≦δ<0),

CsPb _(1-a) Na _a Br _(3+δ) (0<a≦0.7,-0.7≦δ<0), CsPb _(1-a) Li _a Br _(3+δ) (0<a≦0.7, -0.7≦δ<0),

CH ₃ NH ₃ Pb _(1-a) Na _a Br _(3+δ-y) I _y (0<a≦0.7,-0.7≦δ<0,0<y<3), CH ₃ NH ₃ Pb _{(1 -a)} Li _a Br _(3+δ-y) I _y (0<a≦0.7,-0.7≦δ<0,0<y<3), CH ₃ NH ₃ Pb _(1-a) Na _a Br _{( 3+δ-y)} Cl _y (0<a≦0.7,-0.7≦δ<0,0<y<3), CH ₃ NH ₃ Pb _(1-a) Li _a Br _(3+δ-y) Cl _y (0<a≦0.7,-0.7≦δ<0,0<y<3),

(H ₂ N=CH-NH ₂ )Pb _(1-a) Na _a Br _(3+δ) (0<a≦0.7,-0.7≦δ<0), (H ₂ N=CH-NH ₂ )Pb _(1-a) Li _a Br _(3+δ) (0<a≦0.7,-0.7≦δ<0), (H ₂ N=CH-NH ₂ )Pb _(1-a) Na _a Br _{(3+ δ-y)} I _y (0<a≦0.7,-0.7≦δ<0,0<y<3), (H ₂ N=CH-NH ₂ )Pb _(1-a) Na _a Br _{(3+δ -y)} Cl _y (0<a≦0.7,-0.7≦δ<0,0<y<3),

CsPbBr ₃ , CsPbCl ₃ , CsPbI ₃ , CsPbBr _(3-y) I _y (0<y<3), CsPbBr _(3-y) Cl _y (0<y<3), CH ₃ NH ₃ PbBr _{(3-y )} Cl _y (0<y<3),

CH ₃ NH ₃ Pb _(1-a) Zn _a Br ₃ (0<a≦0.7), CH ₃ NH ₃ Pb _(1-a) Al _a Br _(3+δ) (0<a≦0.7, 0≦δ ≦0.7), CH ₃ NH ₃ Pb _(1-a) Co _a Br ₃ (0<a≦0.7), CH ₃ NH ₃ Pb _(1-a) Mn _a Br ₃ (0<a≦0.7), CH ₃ NH ₃ Pb _(1-a) Mg _a Br ₃ (0<a≦0.7),

CsPb _(1-a) Zn _a Br ₃ (0<a≦0.7), CsPb _(1-a) Al _a Br _(3+δ) (0<a≦0.7, 0<δ≦0.7), CsPb _{(1- a)} Co _a Br ₃ (0<a≦0.7), CsPb _(1-a) Mn _a Br ₃ (0<a≦0.7), CsPb _(1-a) Mg _a Br ₃ (0<a≦0.7),

CH ₃ NH ₃ Pb _(1-a) Zn _a Br _(3-y) I _y (0<a≦0.7, 0<y<3), CH ₃ NH ₃ Pb _(1-a) Al _a Br _{(3+ δ-y)} I _y (0<a≦0.7,0<δ≦0.7,0<y<3), CH ₃ NH ₃ Pb _(1-a) Co _a Br _(3-y) I _y (0<a ≦0.7, 0<y<3), CH ₃ NH ₃ Pb _(1-a) Mn _a Br _(3-y) I _y (0<a≦0.7,0<y<3), CH ₃ NH ₃ Pb _{( 1-a)} Mg _a Br _(3-y) I _y (0<a≦0.7, 0<y<3), CH ₃ NH ₃ Pb _(1-a) Zn _a Br _(3-y) Cl _y (0 <a≦0.7, 0<y<3), CH ₃ NH ₃ Pb _(1-a) Al _a Br _(3+δ-y) Cl _y (0<a≦0.7, 0<δ≦0.7, 0<y <3), CH ₃ NH ₃ Pb _(1-a) Co _a Br _(3+δ-y) Cl _y (0<a≦0.7, 0<y<3), CH ₃ NH ₃ Pb _(1-a) Mn _a Br _(3-y) Cl _y (0<a≦0.7, 0<y<3), CH ₃ NH ₃ Pb _(1-a) Mg _a Br _(3-y) Cl _y (0<a≦0.7 , 0<y<3),

(H ₂ N=CH-NH ₂ )Zn _a Br ₃ (0<a≦0.7), (H ₂ N=CH-NH ₂ )Mg _a Br ₃ (0<a≦0.7), (H ₂ N=CH -NH ₂ )Pb _(1-a) Zn _a Br _(3-y) I _y (0<a≦0.7, 0<y<3), (H ₂ N=CH-NH ₂ )Pb _(1-a) Zn _a Br _(3-y) Cl _y (0<a≦0.0<y<3), etc.

As one aspect of the present invention, as the perovskite compound, as a compound having a three-dimensional perovskite crystal structure represented by ABX _(3+δ), CsPbBr ₃ , CsPbBr _(3-y) I _y (0 <y<3).

Specific examples of the perovskite compound having a two-dimensional perovskite crystal structure represented by A ₂ BX _(4+δ) include (C ₄ H ₉ NH ₃ ) ₂ PbBr ₄ , (C ₄ H ₉ NH ₃ ) ₂ PbCl ₄ , (C ₄ H ₉ NH ₃ ) ₂ PbI ₄ , (C ₇ H ₁₅ NH ₃ ) ₂ PbBr ₄ , (C ₇ H ₁₅ NH ₃ ) ₂ PbCl ₄ , (C ₇ H ₁₅ NH ₃ ) ₂ PbI ₄ , (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Li _a Br _(4+δ) (0<a≦0.7, -0.7≦δ<0), (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Na _a Br _(4+δ) (0<a≦0.7, -0.7≦δ<0), (C ₄ H ₉ NH ₃ ) ₂ Pb _{(1-a )} Rb _a Br _(4+δ) (0<a≦0.7, -0.7≦δ<0),

(C ₇ H ₁₅ NH ₃ ) ₂ Pb _(1-a) Na _a Br _(4+δ) (0<a≦0.7, -0.7≦δ<0), (C ₇ H ₁₅ NH ₃ ) ₂ Pb _{(1 -a)} Li _a Br _(4+δ) (0<a≦0.7, -0.7≦δ<0), (C ₇ H ₁₅ NH ₃ ) ₂ Pb _(1-a) Rb _a Br _(4+δ) ( 0<a≦0.7, -0.7≦δ<0),

(C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Na _a Br _(4+δ-y) I _y (0<a≦0.7, -0.7≦δ<0, 0<y<4), (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Li _a Br _(4+δ-y) I _y (0<a≦0.7, -0.7≦δ<0, 0<y<4), (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Rb _a Br _(4+δ-y) I _y (0<a≦0.7, -0.7≦δ<0, 0<y<4),

(C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Na _a Br _(4+δ-y) Cl _y (0<a≦0.7, -0.7≦δ<0, 0<y<4), (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Li _a Br _(4+δ-y) Cl _y (0<a≦0.7, -0.7≦δ<0, 0<y<4), (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Rb _a Br _(4+δ-y) Cl _y (0<a≦0.7, -0.7≦δ<0, 0<y<4),

(C ₄ H ₉ NH ₃ ) ₂ PbBr ₄ , (C ₇ H ₁₅ NH ₃ ) ₂ PbBr ₄ ,

(C ₄ H ₉ NH ₃ ) ₂ PbBr _(4-y) Cl _y (0<y<4), (C ₄ H ₉ NH ₃ ) ₂ PbBr _(4-y) I _y (0<y<4),

(C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Zn _a Br ₄ (0<a≦0.7), (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Mg _a Br ₄ (0<a ≦0.7), (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Co _a Br ₄ (0<a≦0.7), (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Mn _a Br ₄ (0<a≦0.7),

(C ₇ H ₁₅ NH ₃ ) ₂ Pb _(1-a) Zn _a Br ₄ (0<a≦0.7), (C ₇ H ₁₅ NH ₃ ) ₂ Pb _(1-a) Mg _a Br ₄ (0<a ≦0.7), (C ₇ H ₁₅ NH ₃ ) ₂ Pb _(1-a) Co _a Br ₄ (0<a≦0.7), (C ₇ H ₁₅ NH ₃ ) ₂ Pb _(1-a) Mn _a Br ₄ (0<a≦0.7),

(C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Zn _a Br _(4-y) I _y (0<a≦0.7, 0<y<4), (C ₄ H ₉ NH ₃ ) ₂ Pb _{( 1-a)} Mg _a Br _(4-y) I _y (0<a≦0.7, 0<y<4), (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Co _a Br _{(4-y )} I _y (0<a≦0.7, 0<y<4), (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Mn _a Br _(4-y) I _y (0<a≦0.7, 0 <y<4),

(C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Zn _a Br _(4-y) Cl _y (0<a≦0.7, 0<y<4), (C ₄ H ₉ NH ₃ ) ₂ Pb _{( 1-a)} Mg _a Br _(4-y) Cl _y (0<a≦0.7, 0<y<4), (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Co _a Br _{(4-y )} Cl _y (0<a≦0.7, 0<y<4), (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Mn _a Br _(4-y) Cl _y (0<a≦0.7, 0 <y<4) etc.

· Luminescence Spectrum

Perovskite compounds are light emitters that can fluoresce in the visible wavelength region.

When X is a bromide ion, the perovskite compound can emit light in a wavelength range of usually 480 nm or more, preferably 500 nm or more, more preferably 510 nm or more, and usually 700 nm or less, preferably 600 nm or less, more preferably 580 nm or less. Fluorescence with a peak of maximum luminous intensity in the range.

The above upper limit and lower limit can be combined arbitrarily.

As another aspect of the present invention, in the case where X is a bromide ion, the perovskite compound can usually emit light in the range of a wavelength range from 480 nm to 700 nm, preferably from 500 nm to 600 nm, more preferably from 510 nm to 580 nm. Fluorescence at the peak of maximum luminous intensity.

When X is an iodide ion, the perovskite compound can emit more than 520nm, preferably more than 530nm, more preferably more than 540nm, and usually less than 800nm, preferably less than 750nm, more preferably less than 730nm. Fluorescence with a peak of maximum luminous intensity.

The above upper limit and lower limit can be combined arbitrarily.

As another aspect of the present invention, in the case where X is an iodide ion, the perovskite compound can usually emit light within the range of a wavelength range of 520 nm to 800 nm, preferably 530 nm to 750 nm, more preferably 540 nm to 730 nm. Fluorescence at the peak of maximum luminous intensity.

When X is a chloride ion, the perovskite compound can emit more than 300nm, preferably more than 310nm, more preferably more than 330nm, and usually less than 600nm, preferably less than 580nm, more preferably less than 550nm. Fluorescence with a peak of maximum luminous intensity.

The above upper limit and lower limit can be combined arbitrarily.

As another aspect of the present invention, in the case where X is a chloride ion, the perovskite compound can usually emit light having a maximum emission within a range of a wavelength range of 300 nm to 600 nm, preferably 310 nm to 580 nm, more preferably 330 nm to 550 nm. Fluorescence with peak luminescence intensity.

The average particle diameter of (1) component contained in the composition of this embodiment will not be specifically limited as long as it has the effect of this invention. In the composition of the present embodiment, the average particle diameter is preferably 1 nm or more, more preferably 2 nm or more, and still more preferably 3 nm or more, from the viewpoint of maintaining the crystal structure of (1) component well. In addition, in the composition of the present embodiment, the average particle diameter of the component (1) is preferably 10 μm or less, more preferably 1 μm or less, and still more preferably 500 nm or less, from the viewpoint that the component (1) is less likely to settle.

The above upper limit and lower limit can be combined arbitrarily.

The average particle size of the component (1) contained in the composition of the present embodiment is not particularly limited, and from the viewpoint that the component (1) hardly settles in the composition and maintains the crystal structure well, the average particle size is preferably 1 nm to 10 μm, more preferably 2 nm to 1 μm, still more preferably 3 nm to 500 nm.

The average particle diameter of (1) component contained in a composition can be measured by SEM or TEM, for example. Specifically, the above-mentioned average particle diameter can be obtained by observing the Feret diameters of the 20 (1) components contained in the above-mentioned composition by TEM or SEM, and calculating the average Feret diameter which is the average value thereof.

The median diameter (D ₅₀ ) of the component (1) contained in the composition of the present embodiment is not particularly limited as long as it has the effect of the present invention. In the composition according to the present embodiment, from the viewpoint that component (1) maintains a crystal structure well, the median diameter (D ₅₀ ) of component (1) is preferably 3 nm or more, more preferably 4 nm or more, and still more preferably 5nm or more. In addition, in the composition of the present embodiment, the median diameter (D ₅₀ ) of component (1) is preferably 5 μm or less, more preferably 500 nm or less, and still more preferably 100 nm, from the viewpoint that component (1) is less likely to settle. the following.

As another aspect of the present invention, the component (1) contained in the composition preferably has a median particle diameter (D ₅₀ ) of 3 nm to 5 μm, more preferably 4 nm to 500 nm, and still more preferably 5 nm to 100 nm.

In this specification, the median diameter of the (1) component contained in a composition can be measured by TEM, SEM, for example. Specifically, the Feret diameters of the 20 (1) components contained in the composition can be observed by TEM or SEM, and the median diameter (D ₅₀ ) can be obtained from their distribution.

<<(1)-1 ingredient>>

Component (1)-1 is a perovskite compound having an emission peak wavelength different from that of the above-mentioned component (1). In the present embodiment, the difference between the emission peak wavelength of component (1)-1 and the emission peak wavelength of the above-mentioned component (1) when measured under the following conditions is preferably 70 nm or more, more preferably 75 nm or more, particularly preferably 80 nm above. In addition, it is preferably 140 nm or less, more preferably 135 nm or less, and particularly preferably 130 nm or less. The above upper limit and lower limit of the difference in emission peak wavelength may be combined arbitrarily.

As one aspect of the present invention, the difference between the emission peak wavelength of component (1)-1 and the emission peak wavelength of the above-mentioned component (1) when measured under the following conditions is preferably 70 nm or more and 140 nm or less, more preferably 75 nm or more and 135 nm or less , particularly preferably not less than 80 nm and not more than 130 nm.

·Measurement conditions

The emission spectra of components (1) and (1)-1 can be measured using an absolute PL quantum yield measurement device (for example, "C9920-02" manufactured by Hamamatsu Photonics Co., Ltd.), under the conditions of excitation light 450nm, room temperature, and the atmosphere Determination.

<<(2) Ingredients>>

(2) The component is an addition polymerizable compound having an ionic group or a polymer thereof.

The addition polymerizable compound which has an ionic group is an addition polymerizable compound which has an anionic group or a cationic group.

Here, an anionic group refers to a group capable of forming a group having a negative charge or a group having a negative charge, and a cationic group refers to a group capable of forming a group having a positive charge or a group having a positive charge.

In the above-mentioned addition polymerizable compound having an ionic group, examples of the anionic group include a group represented by -PO ₄ ^2- , a group represented by -OSO ₃ ^- , a group represented by ^-COO- The group represented by -OSO ₃ ^- is preferred, the group represented by ^-COO- is preferred, and the group represented by ^-COO- is more preferred.

Among the above-mentioned addition polymerizable compounds having an ionic group, examples of the cationic group include an ammonium group, a primary amino group, a phosphonium group, a sulfonium group, an imidazolium group, and a pyridinium group, and may be an ammonium group , primary amino.

In the above-mentioned addition polymerizable compound having an ionic group, the ionic group may be one type, or may contain two or more types.

The above-mentioned addition-polymerizable compound having an ionic group can form a salt, and the counter cation in the anionic group is not particularly limited, and preferred examples include alkali metal cations, alkaline earth metal cations, ammonium cations, and the like.

The counter anion in the cationic group is not particularly limited, and examples include halide ions and carboxylate anions of Br ^- , Cl ^- , I ^- , F ^- .

Among the above-mentioned addition polymerizable compounds having an ionic group, the addition polymerizable compound is a compound polymerized by addition polymerization.

As the addition polymerization, for example, polymerization of terminal double bonds and triple bonds in a compound, or ring-opening polymerization reaction of a cyclic compound can be exemplified. Among the above-mentioned addition polymerizable compounds having an ionic group, the addition polymerizable compound is preferably an ionically polymerizable compound having an ionic group, or a radical polymerizable compound having an ionic group polymerized by radical polymerization A compound, more preferably a radically polymerizable compound having an ionic group.

(radically polymerizable compound having an ionic group)

Among the above-mentioned addition polymerizable compounds having an ionic group, the radically polymerizable compound having an ionic group is a compound that has an ionic group and is polymerized by reacting a radical with a polymerizable functional group. The polymerizable functional group of the free radical reaction includes, for example, a vinyl group and a substituted vinyl group, such as a styryl group, a propenyl group, a methacryl group, an allyl group, etc., and may be a propenyl group, a styryl group, or a styryl group. , Methacryl, or styryl and methacryl.

Among the above-mentioned addition polymerizable compounds having an ionic group, examples of radical polymerizable compounds include acrylates and their derivatives, methacrylates and their derivatives, styrenes and their derivatives, Acrylonitriles and their derivatives, allyl esters of organic carboxylic acids and their derivatives, vinyl esters of organic carboxylic acids and their derivatives, dialkyl fumaric acid and its derivatives, maleic acid Dialkyl esters of itaconic acid and their derivatives, dialkyl esters of itaconic acid and their derivatives, N-vinylamide derivatives of organic carboxylic acids, maleimide and its derivatives, terminal unsaturated hydrocarbons and Its derivatives, etc., and compounds with ionic groups.

Examples of acrylates and their derivatives having ionic groups include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, acrylic acid -Second-butyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, isobornyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, 2-hydroxyethyl acrylate ester, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 2-hydroxyphenyl acrylate, N,N-dimethylacrylamide, N,N-diethyl A compound having an ionic group in part of its structure, such as N-acrylamide and N-acryloylmorpholine.

Examples of methacrylates and their derivatives having ionic groups include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, methacrylic acid n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate, methacrylic acid Isobornyl, Cyclohexyl Methacrylate, Phenyl Methacrylate, Benzyl Methacrylate, 2-Hydroxyethyl Methacrylate, 2-Hydroxypropyl Methacrylate, 3-Hydroxy Methacrylate Propyl ester, 2-hydroxybutyl methacrylate, 2-hydroxyphenylethyl methacrylate, N,N-dimethylmethacrylamide, N,N-diethylmethacrylamide, N - A compound having an ionic group in part of its structure, such as acryloylmorpholine.

Examples of styrene and its derivatives having ionic groups include styrene, 2,4-dimethyl-α-methylstyrene, o-methylstyrene, m-methylstyrene, and p-methylstyrene. Ethylene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 2,6-dimethylstyrene, 3,4-dimethylstyrene, 3,5-dimethylbenzene Ethylene, 2,4,6-trimethylstyrene, 2,4,5-trimethylstyrene, pentamethylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, o-bromostyrene, m-bromostyrene, p-bromostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene , o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, 2-vinylbiphenyl, 3-vinylbiphenyl, 4-vinylbiphenyl, 1-vinylnaphthalene, 2-vinylnaphthalene, 4 -Vinyl-p-terphenyl, 1-vinylanthracene, α-methylstyrene, o-isopropenyltoluene, m-isopropenyltoluene, p-isopropenyltoluene, 2,4-dimethyl-α- Methylstyrene, 2,3-dimethyl-α-methylstyrene, 3,5-dimethyl-α-methylstyrene, p-isopropyl-α-methylstyrene, α-ethyl Compounds having ionic groups in part of their structures, such as phenylstyrene, α-chlorostyrene, dicumylbenzene, and 4-aminostyrene.

Examples of acrylonitrile having an ionic group and its derivatives include acrylonitrile having an ionic group in a part of its structure such as acrylonitrile. As methacrylonitrile and its derivatives which have an ionic group, the compound which has an ionic group in a part of structure, such as methacrylonitrile, is mentioned.

Vinyl esters of organic carboxylic acids having ionic groups and derivatives thereof include compounds having ionic groups in part of their structures, such as vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl benzoate.

Examples of the allyl ester of organic carboxylic acid having an ionic group and its derivatives include compounds having an ionic group in a part of the structure, such as allyl acetate and allyl benzoate.

Examples of dialkyl fumaric acid having an ionic group and derivatives thereof include dimethyl fumarate, diethyl fumarate, diisopropyl fumarate, and di-sec-butyl fumarate. Compounds having ionic groups in part of their structures, such as esters, diisobutyl fumarate, di-n-butyl fumarate, di-2-ethylhexyl fumarate, and dibenzyl fumarate.

As dialkyl esters of maleic acid and derivatives thereof having ionic groups, dimethyl maleate, diethyl maleate, diisopropyl maleate, di-secondary maleate, A compound having an ionic group in a part of its structure, such as butyl ester, diisobutyl maleate, di-n-butyl maleate, di-2-ethylhexyl maleate, and dibenzyl maleate.

Dialkyl esters of itaconic acid having ionic groups and derivatives thereof include dimethyl itaconate, diethyl itaconate, diisopropyl itaconate, di-secondary itaconate, Compounds having an ionic group in a part of the structure such as butyl ester, diisobutyl itaconate, di-n-butyl itaconate, di-2-ethylhexyl itaconate, and dibenzyl itaconate.

Examples of N-vinylamide derivatives of organic carboxylic acids having ionic groups include compounds having ionic groups in part of their structures, such as N-methyl-N-vinylacetamide.

Examples of the maleimide and its derivatives having an ionic group include compounds having an ionic group in part of the structure, such as N-phenylmaleimide and N-cyclohexylmaleimide.

Examples of terminal unsaturated hydrocarbons having ionic groups and derivatives thereof include 1-butene, 1-pentene, 1-hexene, 1-octene, vinylcyclohexane, vinyl chloride, allyl A compound having an ionic group in part of its structure, such as alcohol.

Among the above-mentioned addition-polymerizable compounds having an ionic group, examples of the radical-polymerizable compound having an ionic group include the following: A compound substituted with a group, or a compound in which a part of the carbon atoms of the above-mentioned radically polymerizable compound is substituted with the above-mentioned anionic group.

(Ionically polymerizable compound having an ionic group)

Among the above-mentioned addition polymerizable compounds having an ionic group, the ionically polymerizable compound having an ionic group is a compound that has an ionic group and is polymerized by reacting cations, anions, etc., with a polymerizable functional group, as Examples of polymerizable functional groups that react with ions include epoxy groups and vinyl groups. Examples of ionically polymerizable compounds having ionic groups include acrylates and derivatives thereof, methacrylates and derivatives thereof, styrenes and derivatives thereof, acrylonitriles and derivatives thereof, Allyl esters of organic carboxylic acids and their derivatives, vinyl esters of organic carboxylic acids and their derivatives, dialkyl fumaric acid and its derivatives, dialkyl maleic acid and its derivatives, Dialkyl esters of itaconic acid and their derivatives, N-vinylamide derivatives of organic carboxylic acids, maleimide and its derivatives, terminal unsaturated hydrocarbons and their derivatives, structures of epoxy monomers A compound with an ionic group in a part of it.

Among the above-mentioned addition-polymerizable compounds having an ionic group, examples of the ion-polymerizable compound having an ionic group include substituting a part of the hydrogen atoms of the above-mentioned ion-polymerizable compound with the above-mentioned anionic group. or a compound in which a part of the carbon atoms of the above-mentioned ionically polymerizable compound is substituted with the above-mentioned anionic group.

Part or all of the above-mentioned addition-polymerizable compound having an ionic group may be adsorbed on the surface of the perovskite compound of the present invention, or may be dispersed in the composition.

Among the above-mentioned addition polymerizable compounds having ionic groups, examples of polymerizable compounds having anionic groups or salts having counter cations include barium acrylate, potassium 3-sulfopropyl methacrylate, 3 -[[2-(methacryloyloxy)ethyl]dimethylammonium]propionate, 2-(methacryloyloxy)ethyl 2-(trimethylamino)ethyl phosphate, 2-acrylamide-2-methylpropanesulfonic acid, sodium vinylsulfonate, vinylsulfonic acid, sodium p-styrenesulfonate hydrate, sodium 4-vinylbenzenesulfinate, 4-carboxystyrene, 3 - allyloxypropionic acid, acrylic acid, methacrylic acid, also acrylic acid, methacrylic acid, 2-acrylamide-2-methylpropanesulfonic acid, 4-carboxystyrene, 3-[[2-(methacrylic acid Acryloyloxy) ethyl] dimethyl ammonium] propionate, which can be methacrylic acid, 2-acrylamide-2-methylpropanesulfonic acid, 4-carboxystyrene, 3-[[2-( Methacryloxy)ethyl]dimethylammonium]propionate, but also methacrylic acid, 4-carboxystyrene, 3-[[2-(methacryloxy)ethyl]di Methylammonium] propionate.

Among the above-mentioned addition polymerizable compounds having ionic groups, examples of polymerizable compounds having cationic groups or salts having counter anions include trimethyl-2-methacryloyloxyethyl chloride Ammonium, 2-(methacryloyloxy)ethyl 2-(trimethylamino)ethyl phosphate, 3-[[2-(methacryloyloxy)ethyl]dimethylammonium]propane Ester, (3-acrylamidopropyl) trimethyl ammonium chloride, trimethyl vinyl ammonium bromide, 4-vinylbenzylamine, 3-aminopropene hydrochloride, glycidyl trimethyl chloride Ammonium can also be 4-vinylbenzylamine, 3-[[2-(methacryloyloxy)ethyl]dimethylammonium]propionate.

The above-mentioned addition polymerizable compound having an ionic group can be polymerized by a method described later to form a polymer having an ionic group.

The addition-polymerizable compound having an ionic group contained in the composition of the embodiment may be a polymer of the above-mentioned addition-polymerizable compound having an ionic group polymerized by a method described later.

The so-called polymerization means that in at least a part of polymerizable functional groups such as vinyl groups, acryloyl groups, methacryloyl groups, allyl groups, and epoxy groups contained in addition polymerizable compounds having ionic groups, the The free radicals or ions generated by the polymerization initiator etc. react to form a polymer.

As the polymer of the addition polymerizable compound having an ionic group, for example, polystyrene resin, polyvinyl resin, polyacrylic resin, polymethacrylic resin, polymethacrylic resin, Polyallyl resin, epoxy resin.

<<(3) Ingredients>>

(3) The component is a solvent. The solvent is not particularly limited as long as it is a medium capable of dispersing the above-mentioned (1) component, but a solvent that hardly dissolves the (1) component is preferable.

In this specification, a "solvent" refers to a substance that is in a liquid state at 1 atm and 25° C. (except for polymerizable compounds and polymers).

In the present specification, "dispersion" refers to a state in which (1) components, aggregates, and the like float or suspend in solvents, polymerizable compounds, polymers, and the like, and may partially settle.

Examples of solvents include esters such as methyl formate, ethyl formate, propyl formate, amyl formate, methyl acetate, ethyl acetate, and amyl acetate; γ-butyrolactone, acetone, dimethyl ketone, diiso Ketones such as butyl ketone, cyclopentanone, cyclohexanone and methylcyclohexanone; diethyl ether, methyl tert-butyl ether, diisopropyl ether, dimethoxymethane, dimethoxyethane, 1, 4-dioxane, 1,3-dioxolane, 4-methyldioxolane, tetrahydrofuran, methyltetrahydrofuran, anisole and phenetole ethers; methanol, ethanol, 1-propanol, 2-propanol alcohol, 1-butanol, 2-butanol, tert-butanol, 1-pentanol, 2-methyl-2-butanol, methoxypropanol, diacetone alcohol, cyclohexanol, 2-fluoroethanol, 2,2,2-Trifluoroethanol and 2,2,3,3-tetrafluoro-1-propanol and other alcohols; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethyl Glycol ethers such as glycol monoethyl ether acetate and triethylene glycol dimethyl ether; N-methyl-2-pyrrolidone, N,N-dimethylformamide, acetamide, N,N-dimethylethyl ether Organic solvents with amide groups such as amides; organic solvents with nitrile groups such as acetonitrile, isobutyronitrile, propionitrile, and methoxyacetonitrile; organic solvents with carbonate groups such as ethylene carbonate and propylene carbonate; Organic solvents with halogenated hydrocarbon groups such as methane and chloroform; organic solvents with hydrocarbon groups such as n-pentane, cyclohexane, n-hexane, benzene, toluene, and xylene; dimethyl sulfoxide, 1-octadecene, etc.

Among them, methyl formate, ethyl formate, propyl formate, pentyl formate, methyl acetate, ethyl acetate, pentyl acetate and other esters; γ-butyrolactone, acetone, dimethyl ketone, diisobutyl ketone , cyclopentanone, cyclohexanone, methyl cyclohexanone and other ketones; diethyl ether, methyl tert-butyl ether, diisopropyl ether, dimethoxymethane, dimethoxyethane, 1,4-di Oxane, 1,3-dioxolane, 4-methyldioxolane, tetrahydrofuran, methyltetrahydrofuran, anisole, phenetole and other ethers; acetonitrile, isobutyronitrile, propionitrile, methoxyacetonitrile, etc. have Organic solvents with nitrile groups; organic solvents with carbonate groups such as ethylene carbonate and propylene carbonate; organic solvents with halogenated hydrocarbon groups such as methylene chloride and chloroform; n-pentane, cyclohexane, n-hexane, benzene , toluene, xylene and other organic solvents with hydrocarbon groups, considering the low polarity and difficulty in dissolving the (1) component, organic solvents with halogenated hydrocarbon groups such as dichloromethane and chloroform are preferred; n-pentane, cyclohexane, n-hexane Alkanes, benzene, toluene, xylene and other organic solvents with hydrocarbon groups.

<<(4) Ingredients>>

(4) The component is a polymeric compound or polymer other than the above-mentioned (2) component.

The polymeric compound other than the said (2) component means the polymeric compound which does not have an ionic group.

The polymerizable compound other than the above-mentioned (2) component contained in the composition of this embodiment will not be specifically limited as long as it has the effect of this invention, One type or two types may be sufficient. As a polymeric compound, the polymeric compound whose solubility of (1) component is low at the temperature which manufactures the composition of this embodiment is preferable.

In this specification, a "polymerizable compound" refers to a compound having a monomer having a polymerizable group.

For example, when the composition of this embodiment is produced at room temperature and normal pressure, the polymerizable compound other than the above-mentioned (2) component is not particularly limited, and examples thereof include styrene, acrylate, methacrylate, acrylonitrile and other known polymerizable compounds other than the above-mentioned (2) component. Among them, as the polymerizable compound other than the above-mentioned (2) component, either or both of acrylate and methacrylate which are monomer components of the acrylic resin are preferable.

The polymers other than the above-mentioned (2) component contained in the composition of the present embodiment are not particularly limited, and may be one type or two types. As a polymer, it is preferable that the solubility of (1) component is low at the temperature which manufactures the composition of this embodiment.

For example, when the composition of the present embodiment is produced at room temperature and normal pressure, the polymer other than the above-mentioned (2) component is not particularly limited, and examples thereof include polystyrene, acrylic resin, epoxy resin, and other known polymers. polymer. Among these, acrylic resins are preferred as the polymer. Acrylic resins contain structural units derived from either or both of acrylate and methacrylate.

In the composition of this embodiment, any one or both of acrylate and methacrylate, and those derived from When the structural unit is represented by mol%, it may be 10 mol% or more, 30 mol% or more, 50 mol% or more, 80 mol% or more, or 100 mol%.

The weight average molecular weight of the polymer is preferably 100-1200,000, more preferably 1,000-800,000, and still more preferably 5,000-150,000.

In this specification, a "weight average molecular weight" means the polystyrene conversion value measured by the gel permeation chromatography (GPC) method.

<<(5) Ingredients>>

(5) The component is at least one compound or ion selected from ammonia, amines, carboxylic acids, and their salts or ions.

Examples of the component (5) include ammonia, amine, and carboxylic acid, and forms available as the above-mentioned compounds, and at least one compound or ion selected from these salts or ions.

That is, the component (5) may be at least one compound selected from the group consisting of ammonia, amine, carboxylic acid, ammonia salt, amine salt, carboxylic acid salt, ammonia ion, amine ion, and carboxylic acid ion, or ion.

Ammonia, amines, and carboxylic acids, as well as their salts or ions, typically function as capped ligands. The "capped ligand" is a compound that adsorbs on the surface of the component (1) to stably disperse the component (1) in the composition. Ions or salts (ammonium salts, etc.) of ammonia or amines include ammonium cations represented by general formula (A1) described later and ammonium salts containing the ammonium cations. Examples of carboxylic acid ions or salts (such as carboxylate) include carboxylate anions represented by general formula (A2) described later and carboxylate salts containing them. The composition of this embodiment may contain any one of ammonium salt etc., carboxylate etc., and may contain both.

(5) The component may be an ammonium cation represented by the general formula (A1) or an ammonium salt containing the ammonium cation.

[Chem 2]

In the general formula (A1), R ¹ to R ³ represent a hydrogen atom, and R ⁴ represents a hydrogen atom or a monovalent hydrocarbon group. The hydrocarbon group represented by R ⁴ may be a saturated hydrocarbon group (that is, an alkyl group or a cycloalkyl group) or an unsaturated hydrocarbon group.

The alkyl group represented by R ⁴ may be linear or branched.

The number of carbon atoms of the alkyl group represented by R ⁴ is usually 1-20, preferably 5-20, more preferably 8-20.

The cycloalkyl group represented by R ⁴ may have an alkyl group as a substituent. The number of carbon atoms in the cycloalkyl group is usually 3-30, preferably 3-20, more preferably 3-11. The number of carbon atoms includes the number of carbon atoms of the substituent.

The unsaturated hydrocarbon group of R ⁴ may be linear or branched.

The number of carbon atoms in the unsaturated hydrocarbon group of R ⁴ is usually 2-20, preferably 5-20, more preferably 8-20.

R ⁴ is preferably a hydrogen atom, an alkyl group or an unsaturated hydrocarbon group. As the unsaturated hydrocarbon group, an alkenyl group is preferable. R ⁴ is preferably an alkenyl group having 8 to 20 carbon atoms.

Specific examples of the alkyl group for R ⁴ include the alkyl groups exemplified for R ⁶ to R ⁹ .

Specific examples of the cycloalkyl group for R ⁴ include the cycloalkyl groups exemplified for R ⁶ to R ⁹ .

As the alkenyl group of R ⁴ , among the above-mentioned straight-chain or branched-chain alkyl groups exemplified for R ⁶ to R ⁹ , any single bond (CC) between carbon atoms is substituted with a double bond (C=C). For the alkenyl group, the position of the double bond is not limited.

Preferred examples of such alkenyl include vinyl, propenyl, 3-butenyl, 2-butenyl, 2-pentenyl, 2-hexenyl, 2-nonenyl, 2 -dodecenyl, 9-octadecenyl.

When the ammonium cation forms a salt, the counter anion is not particularly limited, but preferred examples include halide ions of Br ^- , Cl ^- , I ^- , F ^- , carboxylate ions, and the like.

As an ammonium salt having an ammonium cation represented by the general formula (A1) and a counter anion, n-octyl ammonium salt and oleyl ammonium salt are mentioned as a preferable example.

(5) The component may be a carboxylate anion represented by general formula (A2) or a carboxylate containing it.

R ⁵ ―CO ₂ ^- ···(A2)

In the general formula (A2), R ⁵ represents a monovalent hydrocarbon group. The hydrocarbon group represented by R ⁵ may be a saturated hydrocarbon group (ie, an alkyl group, a cycloalkyl group) or an unsaturated hydrocarbon group.

The alkyl group represented by R ⁵ may be linear or branched. The number of carbon atoms of the alkyl group represented by R ⁵ is usually 1-20, preferably 5-20, more preferably 8-20.

The cycloalkyl group represented by R ⁵ may have an alkyl group as a substituent. The number of carbon atoms in the cycloalkyl group is usually 3-30, preferably 3-20, more preferably 3-11. The number of carbon atoms also includes the number of carbon atoms of the substituent.

The unsaturated hydrocarbon group represented by R ⁵ may be linear or branched.

The number of carbon atoms in the unsaturated hydrocarbon group represented by R ⁵ is usually 2-20, preferably 5-20, more preferably 8-20.

R ⁵ is preferably an alkyl group or an unsaturated hydrocarbon group. As the unsaturated hydrocarbon group, an alkenyl group is preferable.

Specific examples of the alkyl group of R ⁵ include the alkyl groups exemplified for R ⁶ to R ⁹ .

Specific examples of the cycloalkyl group for R ⁵ include the cycloalkyl groups exemplified for R ⁶ to R ⁹ .

Specific examples of the alkenyl group for R ⁵ include the alkenyl groups exemplified for R ⁴ .

The carboxylate anion represented by the general formula (A2) is preferably an oleic acid anion.

When a carboxylate anion forms a salt, the counter cation is not particularly limited, but preferred examples include alkali metal cations, alkaline earth metal cations, ammonium cations, and the like.

<<(6) Ingredients>>

(6) The component is one or more compounds selected from the group consisting of an organic compound having an amino group, an alkoxy group, and a silicon atom, and a silazane or a modified product thereof.

(Organic compounds having amino, alkoxy and silicon atoms)

The compositions of the present invention may contain organic compounds having amino groups, alkoxy groups and silicon atoms.

In addition, the organic compound having an amino group, an alkoxy group, and a silicon atom may not contain either or both of an ionic group and an addition polymerizable group.

The organic compound having an amino group, an alkoxy group, and a silicon atom may be an organic compound having an amino group, an alkoxy group, and a silicon atom represented by the following formula (A5-5).

The organic compound represented by the following general formula (A5-5) has an amino group and an alkoxysilyl group.

[Chem 3]

In the general formula (A5-5), A is a divalent hydrocarbon group, O is an oxygen atom, N is a nitrogen atom, Si is a silicon atom, and R ²² to R ²³ independently represent a hydrogen atom, an alkyl group or a cycloalkyl group, R ²⁴ represents an alkyl group or a cycloalkyl group, and R ²⁵ to R ²⁶ represent a hydrogen atom, an alkyl group, an alkoxy group or a cycloalkyl group.

The alkyl group for R ²² to R ²⁶ may be linear or branched.

The number of carbon atoms in the alkyl group is usually 1-20, preferably 5-20, more preferably 8-20.

The cycloalkyl group for R ²² to R ²⁶ may have an alkyl group as a substituent. The number of carbon atoms in the cycloalkyl group is usually 3-30, preferably 3-20, more preferably 3-11. The number of carbon atoms includes the number of carbon atoms of the substituent.

Specific examples of the alkyl group for R ²² to R ²⁶ include the alkyl groups exemplified for R ⁶ to R ⁹ .

Specific examples of the cycloalkyl group for R ²² to R ²⁶ include the cycloalkyl groups exemplified for R ⁶ to R ⁹ .

Examples of the alkoxy group for R ²⁵ to R ²⁶ include a monovalent group in which the linear or branched alkyl group exemplified by R ⁶ to R ⁹ is bonded to an oxygen atom.

Examples of the alkoxy group for R ²⁵ to R ²⁶ include methoxy, ethoxy, butoxy and the like, preferably methoxy.

The divalent hydrocarbon group represented by A may be any group obtained by removing two hydrogen atoms from a hydrocarbon compound, and the hydrocarbon compound may be an aliphatic hydrocarbon, an aromatic hydrocarbon, or a saturated aliphatic hydrocarbon. When A is an alkylene group, it may be linear or branched. The number of carbon atoms in the alkylene group is usually 1-100, preferably 1-20, more preferably 1-5.

Part or all of the organic compound having an amino group, an alkoxy group, and a silicon atom represented by the general formula (A5-5) may be adsorbed on the surface of the component (1) of the present invention, or may be dispersed in the composition .

As an organic compound having an amino group, an alkoxy group and a silicon atom represented by the general formula (A5-5), trimethoxy[3-(methylamino)propyl]silane, 3-aminopropyltriethoxy Silane, 3-aminopropyldimethoxymethylsilane, 3-aminopropyldiethoxymethylsilane, 3-aminopropyltrimethoxysilane, more preferably 3-aminopropyltrimethoxysilane.

As an organic compound having an amino group, an alkoxy group and a silicon atom, preferably in the organic compound represented by the above-mentioned general formula (A5-5), R ²² and R ²³ are hydrogen atoms, R ²⁴ is the above-mentioned alkyl group, R ²⁵ and A compound in which R ²⁶ is an alkoxy group.

(silazane or its modified form)

The composition of the present invention may contain silazane or a modified product thereof.

Silazanes are compounds having Si-N-Si bonds.

Silazane may be linear, branched or cyclic. In addition, silazane may be low-molecular or high-molecular (in this specification, it may be described as polysilazane.).

In this specification, "low molecular weight silazane" means a silazane with an index average molecular weight of less than 600, and "high molecular weight silazane (polysilazane)" means a silazane with an index average molecular weight of 600 to 2000.

In this specification, a "number average molecular weight" means the polystyrene conversion value measured by the gel permeation chromatography (GPC) method.

For example, low-molecular-weight silazanes represented by the following general formula (B1) or (B2), and polysilazanes having a structural unit represented by the general formula (B3) or a structure represented by the general formula (B4) are preferred. alkyl.

It is also possible to modify the silazane by the method described later, and use it after modifying it with silicon oxide.

The silazane contained in the composition of the embodiment may be a modified silazane modified by a method described later.

Modification refers to replacing N with O in at least a part of the Si-N-Si bond contained in silazane to form a Si-O-Si bond. The modified body of silazane contains Si-O-Si bond compound of.

As a modified form of silazane, for example, a low-molecular compound in which at least one N contained in the above-mentioned general formula (B1) or (B2) is replaced by O, and a low-molecular compound having a structural unit represented by the general formula (B3) A polymer compound in which at least one N contained in polysilazane is replaced by O, or a polymer in which at least one N contained in polysilazane having a structure represented by the general formula (B4) is replaced by O compound.

The ratio of the number of substituted Os to the total amount of N contained in the general formula (B2) is preferably 0.1 to 100%, more preferably 10 to 98%, and still more preferably 30 to 95%.

The ratio of the number of substituted Os to the total amount of N contained in the general formula (B3) is preferably 0.1 to 100%, more preferably 10 to 98%, and still more preferably 30 to 95%.

The ratio of the number of substituted Os to the total amount of N contained in the general formula (B4) is preferably 0.1 to 99%, more preferably 10 to 97%, and even more preferably 30 to 95%.

The modified form of silazane may be one kind or a mixture of two or more kinds.

The number of Si atoms, the number of N atoms, and the number of O atoms contained in silazane and its modified body can be determined by nuclear magnetic resonance spectroscopy (NMR), X-ray photoelectron spectroscopy (XPS), or using a transmission electron microscope ( TEM) energy dispersive X-ray analysis (EDX) and other calculations.

As a particularly preferable method, it can be calculated by measuring the number of Si atoms, the number of N atoms, and the number of O atoms in the composition by X-ray photoelectron spectroscopy (XPS).

The ratio of the number of O atoms to the number of N atoms contained in silazane and its modified product measured by the above method is preferably 0.1 to 99%, more preferably 10 to 95%, and still more preferably 30 to 90%.

At least a part of the silazane or its modified form may be adsorbed on the perovskite compound contained in the composition, or may be dispersed in the composition.

[chemical 4]

In the general formula (B1), R ¹⁴ and R ¹⁵ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, An aryl group having 6 to 20 carbon atoms, or an alkylsilyl group having 1 to 20 carbon atoms. An alkyl group with 1 to 20 carbon atoms, an alkenyl group with 1 to 20 carbon atoms, a cycloalkyl group with 3 to 20 carbon atoms, an aryl group with 6 to 20 carbon atoms, or a carbon number of The alkylsilyl group of 1 to 20 may have a substituent such as an amino group. A plurality of R ¹⁵ may be the same or different.

Examples of the low-molecular-weight silazane represented by the general formula (B1) include 1,3-divinyl-1,1,3,3-tetramethyldisilazane, 1,3-diphenyltetra Methyldisilazane and 1,1,1,3,3,3-hexamethyldisilazane.

[chemical 5]

In the general formula (B2), R ¹⁴ and R ¹⁵ are the same as above.

A plurality of R ¹⁴ may be the same or different.

A plurality of R ¹⁵ may be the same or different.

n represents not less than 1 and not more than 20. n may be 1 or more and 10 or less, and may be 1 or 2.

Examples of the low-molecular-weight silazane represented by the general formula (B2) include octamethylcyclotetrasilazane, 2,2,4,4,6,6-hexamethylcyclotrisilazane and 2, 4,6-Trimethyl-2,4,6-trivinylcyclotrisilazane.

As the low molecular weight silazane, octamethylcyclotetrasilazane and 1,3-diphenyltetramethyldisilazane are preferable, and octamethylcyclotetrasilazane is more preferable.

Polysilazane is a polymer compound having a Si-N-Si bond, and is not particularly limited, and examples thereof include polymer compounds having a structural unit represented by the following general formula (B3). The structural unit represented by the general formula (B3) contained in polysilazane may be 1 type or multiple types.

[chemical 6]

In the general formula (B3), R ¹⁴ and R ¹⁵ are the same as above.

A plurality of R ¹⁴ may be the same or different.

A plurality of R ¹⁵ may be the same or different.

m represents an integer of 2 or more and 10000 or less.

The polysilazane having the structural unit represented by the general formula (B3) may be, for example, perhydropolysilazane in which R ¹⁴ and R ¹⁵ are all hydrogen atoms.

In addition, the polysilazane having a structural unit represented by the general formula (B3) may be, for example, an organopolysilazane in which at least one R ¹⁵ is a group other than a hydrogen atom. Depending on the application, perhydropolysilazane and organopolysilazane can be appropriately selected or used in combination.

Polysilazane may have a ring structure partly in the molecule, for example, may have a structure represented by general formula (B4).

[chemical 7]

n ₂ represents an integer of 1 to 10000. n ₂ may be 1 or more and 10 or less, and may be 1 or 2.

Silazane or a modified product thereof is not particularly limited, but organopolysilazane or a modified product thereof is preferable from the viewpoint of improving dispersibility and suppressing aggregation. The organopolysilazane can be, for example, an organopolysilazane having a structural unit represented by the general formula (B3), wherein at least one of ^R14 and ^R15 in the general formula (B3) has a carbon number of 1 to An alkyl group with 20 carbon atoms, an alkenyl group with 1 to 20 carbon atoms, a cycloalkyl group with 3 to 20 carbon atoms, an aryl group with 6 to 20 carbon atoms, or an alkyl group with 1 to 20 carbon atoms Silyl. In addition, it may be an organopolysilazane having a structure represented by the general formula (B4), wherein at least one bond in the general formula (B4) is bonded to ^R14 or ^R15 , and the above-mentioned ^R14 and ^R15 At least one of them is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms , or an alkylsilyl group having 1 to 20 carbon atoms.

The organopolysilazane is preferably an organopolysilazane having a structural unit represented by the general formula (B3), wherein at least one of ^R14 and ^R15 in the general formula (B3) is a methyl group, or preferably has The polysilazane of the structure shown in the general formula (B4), wherein at least one bonding bond in the general formula (B4) is bonded to R ¹⁴ or R ¹⁵ , at least one of the R ¹⁴ and R ¹⁵ is formazan base.

Preferred are organopolysilazanes in which at least a portion of R ¹⁴ or R ¹⁵ is methyl.

A general polysilazane has, for example, a linear structure and a ring structure such as a 6-membered ring or an 8-membered ring. As mentioned above, its molecular weight is 600-2000 (polystyrene conversion) in terms of number average molecular weight (Mn), and it can be liquid or solid according to molecular weight. Commercially available products can be used for the above polysilazane, and examples of commercially available products include NN120-10, NN120-20, NAX120-20, NN110, NAX120, NAX110, NL120A, NL110A, NL150A, NP110, NP140 (AZ Electronic Materials Co., Ltd. ) and AZNN-120-20, Durazane (registered trademark) 1500 SlowCure, Durazane (registered trademark) 1500 RapidCure, Durazane (registered trademark) 1800 (MerkerForm Materials Co., Ltd.), and Durazane (registered trademark) 1033 (MerkerForm Materials Co., Ltd.) wait.

The polysilazane having a structural unit represented by the general formula (B3) is preferably AZNN-120-20, Durazane (registered trademark) 1500 SlowCure, Durazane (registered trademark) 1500 RapidCure, more preferably Durazane (registered trademark) 1500 SlowCure.

<Compounding ratio of each component>

In the composition of this embodiment, the compounding ratio of (1) component and (2) component should just be the grade which can show two luminescence peaks even if 2 types of perovskite compounds are mixed with (2) component, and can be calculated according to (1) The type of component and (2) component etc. are determined suitably.

In the composition of the embodiment, the mass ratio [(1)/(2)] of the component (1) to the component (2) may be 0.001 to 1000, 0.005 to 100, or 0.01 1 or less.

The composition in which the compounding ratio of the component (1) and the component (2) falls within the above range is preferable from the viewpoint of showing two luminescence peaks even if two perovskite compounds are mixed with the component (2).

In the composition of this embodiment, the compounding ratio of (1) component and the total of (3) component and (4) component should just be the grade which can exhibit the luminescence function of (1) component well, and it can be based on (1) ) component, (3) component, type of (4) component, etc. are appropriately determined.

In the composition of the embodiment containing (1) component, (2) component, and at least one selected from (3) component and (4) component, (1) component and (3) component and (4) component The total mass ratio [(1)/(3) and (4) total] may be 0.00001 to 10, 0.0001 to 2, or 0.0005 to 1.

The composition in which the compounding ratio of the component (1) and the total of the components (3) and (4) falls within the above-mentioned range is preferable from the viewpoint that aggregation of the component (1) hardly occurs and luminescence is exhibited well. of.

The present invention provides a composition containing (1) component, (2) component, (5) component and at least one embodiment selected from (3) component and (4) component, or containing (1) component , (2) component, (4') component and (5) component, and the total content ratio of (1) component, (2) component and (4') component is 90% by mass or more with respect to the total mass of the composition In the composition of the mode, the compounding ratio of (1) component and (5) component should just be the degree that can exhibit the luminous effect of (1) component well, can be according to (1) component～(5) kind etc. Sure.

In the composition of the embodiment containing (1) component, (2) component, (5) component and at least one component selected from (3) component and (4) component, (1) component and (5) The molar ratio [(1)/(5)] of the components may be 0.0001 to 1000, or 0.01 to 100.

A composition in which the compounding ratio of the total of the component (1) and the component (5) falls within the above range is preferable from the viewpoint that aggregation of the component (1) hardly occurs and luminescence is exhibited well.

The present invention provides a composition containing (1) component, (2) component, (6) component, and at least one embodiment selected from (3) component and (4) component, or containing (1) Ingredient, (2) component, (4') component and (6) component, and the total content ratio of (1) component, (2) component and (4') component is 90% by mass or more with respect to the total mass of the composition In the composition of the embodiment, the compounding ratio of the component (1) and the component (6) is sufficient as long as the luminescent effect of the component (1) can be exhibited well, and it can be adjusted according to the types of the components (1) to (6). Properly determined.

In the composition of an embodiment containing (1) component, (2) component, (5) component, (6) component, and at least one selected from (3) component and (4) component, as (1) The molar ratio [Si/B] of the metal ion of the B component of the component to the Si element of the (6) component may be 0.001 to 2000, or 0.01 to 500.

A composition in which the compounding ratio of the total of the component (1) and the component (6) falls within the above-mentioned range is preferable from the viewpoint that aggregation of the component (1) hardly occurs and luminescence is exhibited well.

One aspect of the present invention is a composition comprising the above-mentioned (1) component, the above-mentioned (2) component, and the above-mentioned (3) component, which is a perovskite compound represented by CsPbBr for the above-mentioned ( ₁ ) component, and the above-mentioned (2) component is selected from From 4-vinylbenzylamine, 4-carboxystyrene, 2-acrylamide-2-methylpropanesulfonic acid, 3-[[2-(methacryloyloxy)ethyl]dimethylammonium]propane A polymer of at least one addition-polymerizable compound among esters and methacrylic acid, a composition in which the mass ratio [(1)/(2)] of the above-mentioned component (1) to component (2) is 0.001 to 0.100 ( A).

Another aspect of the present invention is a composition comprising the above-mentioned (1) component, the above-mentioned (2) component and the above-mentioned (3) component, wherein the (1) component is composed of CsPbBr _(3-y) I _y (0<y<3) Composition (B) in which the perovskite compound shown, (2) component is a polymer of methacrylic acid, and the mass ratio [(1)/(2)) of (1) component to (2) component is 0.001 to 0.080 .

Still another aspect of the present invention is a composition comprising the above-mentioned (1) component, the above-mentioned (2) component, and the above-mentioned (4′) component, which is a perovskite compound represented by CsPbBr for the above-mentioned ( ₁ ) component, and the above-mentioned (2) The ingredients are selected from 4-vinylbenzylamine, 4-carboxystyrene, 2-acrylamide-2-methylpropanesulfonic acid, 3-[[2-(methacryloyloxy)ethyl]dimethyl A polymer of at least one addition-polymerizable compound of ammonium] propionate and methacrylic acid, wherein the mass ratio [(1)/(2)] of the above-mentioned component (1) to component (2) is 0.001 to 0.050 Composition (C).

In the composition (C), 4-vinylbenzylamine is particularly preferable as the above-mentioned (2) component.

Still another aspect of the present invention is a composition comprising the above-mentioned (1) component, the above-mentioned (2) component, the above-mentioned (3) component, and the above-mentioned (6) component, which is a perovskite compound represented by _CsPbBr3 for the above-mentioned (1) component , the above-mentioned (2) component is selected from 4-vinylbenzylamine, 4-carboxystyrene, 2-acrylamide-2-methylpropanesulfonic acid, 3-[[2-(methacryloyloxy) ethyl base] dimethylammonium] propionate and at least one addition polymerizable compound in methacrylic acid, the mass ratio of the above-mentioned (1) component to the above-mentioned (2) component [(1)/(2) ] is 0.001 to 0.030, and the molar ratio [Si/B] of the metal ion of the B component of the perovskite compound to the Si element of the (6) component is 25 to 125 (D).

In the composition (D), as the above-mentioned (2) component, 4-vinylbenzylamine or methacrylic acid is particularly preferable. In the composition (D), as the above-mentioned component (6), silazane or a modified product thereof is preferable, and polysilazane or a modified product thereof is more preferable.

Still another aspect of the present invention is a composition comprising the above-mentioned (1) component, the above-mentioned (2) component, the above-mentioned (3) component, and the above-mentioned (6) component, wherein the above-mentioned (1) component is composed of CsPbBr _(3-y) I _y The perovskite compound represented by (0<y<3), the above-mentioned (2) component is selected from 4-vinylbenzylamine, 4-carboxystyrene, 2-acrylamide-2-methylpropanesulfonic acid, 3- A polymer of [[2(methacryloyloxy)ethyl]dimethylammonium]propionate and at least one addition-polymerizable compound of methacrylic acid, the above-mentioned (1) component and the above-mentioned (2) A combination in which the mass ratio [(1)/(2)] of the components is 0.001 to 0.060, and the molar ratio [Si/B] of the metal ion of the B component of the perovskite compound to the Si element of the (6) component is 3 to 60 thing (E).

In the composition (E), methacrylic acid is particularly preferable as the above-mentioned (2) component. In the composition (E), as the above-mentioned component (6), silazane or a modified product thereof is preferable, and polysilazane or a modified product thereof is more preferable.

<Manufacturing method of composition>

Hereinafter, regarding the manufacturing method of the composition in this invention, embodiment is shown and demonstrated. According to the manufacturing method of the composition of this embodiment, the composition of embodiment of this invention can be manufactured. In addition, the composition of this invention is not limited to the composition manufactured by the manufacturing method of the composition of the following embodiment.

(1) Production method of perovskite compound containing A, B and X as constituent components

The perovskite compound can be produced by the method of the first embodiment or the second embodiment described below with reference to known documents (Nano Lett. 2015, 15, 3692-3696, ACSNano, 2015, 9, 4533-4542) .

(First embodiment of the method for producing a perovskite compound comprising A, B, and X as constituents)

For example, as the production method of the perovskite compound related to the present invention, a production method including the steps of dissolving component B, component X, and component A in a solvent x to obtain a solution g; A step of mixing the solution g with a solvent y having a lower solubility of the perovskite compound in the solvent than the solvent x used in the step of obtaining the solution g. More specifically, a production method including the steps of dissolving a compound containing component B and component X and a compound containing component A or component A and component X in a solvent x to obtain a solution g; and A step of mixing the obtained solution g with a solvent y having a lower solubility of the perovskite compound in the solvent than the solvent x used in the step of obtaining the solution g.

The perovskite compound is precipitated by mixing the solution g with a solvent y having a lower solubility of the perovskite compound than the solvent x used in the step of obtaining the solution g.

Hereinafter, the production method including the steps of dissolving a compound containing component B and component X, and a compound containing component A or component A and component X in a solvent x to obtain a solution g; and dissolving the obtained A step of mixing the solution g with a solvent y having a lower solubility of the perovskite compound in the solvent than the solvent x used in the step of obtaining the solution g.

In addition, solubility means the solubility at the temperature which performs a mixing process.

From the viewpoint of stably dispersing the perovskite compound, the above-mentioned production method preferably includes a step of adding a capping ligand. Preferably, the capped ligand is added before the above-mentioned mixing process, and the capped ligand can be added to the solution g in which the components A, B and X are dissolved; or the capped ligand can be added to the solvent y, The solvent y is a solvent in which the solubility of the perovskite compound is lower than that of the solvent x used in the process of obtaining the solution g; or the capping ligand may be added to both the solvent x and the solvent y.

The above-mentioned production method preferably includes a step of removing coarse particles by methods such as centrifugation and filtration after the above-mentioned mixing step. The size of the coarse particles removed by the above-mentioned removal step is preferably 10 μm or more, more preferably 1 μm or more, particularly preferably 500 nm or more.

The operation of above-mentioned mixed solution g and solvent y can be (I) the operation that solution g is added dropwise in solvent y, also can be (II) the operation that solvent y is added dropwise in solution g, but from raising (1 (I) is preferable from the viewpoint of the dispersibility of the ) component.

From the viewpoint of improving the dispersibility of (1) component, it is preferable to stir at the time of dripping.

In the step of mixing the solution g and the solvent y, the temperature is not particularly limited, but from the viewpoint of securing the easiness of precipitation of the component (1), it is preferably in the range of -20°C to 40°C, and more preferably -5°C or higher. range below 30°C.

The two solvents x and y having different solubility in the solvent of the perovskite compound used in the above production method are not particularly limited, for example, two solvents selected from the following solvents: methanol, ethanol, 1-propane alcohol, 2-propanol, 1-butanol, 2-butanol, tert-butanol, 1-pentanol, 2-methyl-2-butanol, methoxypropanol, diacetone alcohol, cyclohexanol, 2-fluoroethanol, 2,2,2-trifluoroethanol, 2,2,3,3-tetrafluoro-1-propanol and other alcohols; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono Butyl ether, ethylene glycol monoethyl ether acetate, triethylene glycol dimethyl ether and other glycol ethers; N-methyl-2-pyrrolidone, N, N-dimethylformamide, acetamide, N, N- Organic solvents with amide groups such as dimethylacetamide; methyl formate, ethyl formate, propyl formate, amyl formate, methyl acetate, ethyl acetate, amyl acetate and other esters; γ-butyrolactone, acetone , dimethyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methyl cyclohexanone and other ketones; diethyl ether, methyl tert-butyl ether, diisopropyl ether, dimethoxymethane, di Methoxyethane, 1,4-dioxane, 1,3-dioxolane, 4-methyldioxolane, tetrahydrofuran, methyltetrahydrofuran, anisole, phenetole and other ethers; acetonitrile, isobutyl Nitrile, propionitrile, methoxyacetonitrile and other organic solvents with nitrile groups; ethylene carbonate, propylene carbonate and other organic solvents with carbonate groups; dichloromethane, chloroform and other organic solvents with halogenated hydrocarbon groups; Pentane, cyclohexane, n-hexane, benzene, toluene, xylene and other organic solvents with hydrocarbon groups; dimethyl sulfoxide.

As the solvent x used in the step of obtaining the solution g contained in the above-mentioned production method, a solvent having a high solubility of the perovskite compound in the solvent is preferable, and the above-mentioned step is performed at room temperature (10°C to 30°C), for example For example, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, tert-butanol, 1-pentanol, 2-methyl-2-butanol, methoxy propanol, diacetone alcohol, cyclohexanol, 2-fluoroethanol, 2,2,2-trifluoroethanol, 2,2,3,3-tetrafluoro-1-propanol and other alcohols; ethylene glycol monomethyl Ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, triethylene glycol dimethyl ether and other glycol ethers; N-methyl-2-pyrrolidone, N, N-di Organic solvents with amide groups such as methylformamide, acetamide, N,N-dimethylacetamide; dimethyl sulfoxide.

As the solvent y used in the mixing step included in the above-mentioned production method, a solvent with a low solubility of the perovskite compound in the solvent is preferable. For example, when the above-mentioned step is performed at room temperature (10° C. to 30° C.), Examples include methyl formate, ethyl formate, propyl formate, pentyl formate, methyl acetate, ethyl acetate, pentyl acetate, etc. esters; γ-butyrolactone, acetone, dimethyl ketone, and diisobutyl ketone , cyclopentanone, cyclohexanone, methyl cyclohexanone and other ketones; diethyl ether, methyl tert-butyl ether, diisopropyl ether, dimethoxymethane, dimethoxyethane, 1,4-di Oxane, 1,3-dioxolane, 4-methyldioxolane, tetrahydrofuran, methyltetrahydrofuran, anisole, phenetole and other ethers; acetonitrile, isobutyronitrile, propionitrile, methoxyacetonitrile, etc. have Organic solvents with nitrile groups; organic solvents with carbonate groups such as ethylene carbonate and propylene carbonate; organic solvents with halogenated hydrocarbon groups such as methylene chloride and chloroform; n-pentane, cyclohexane, n-hexane, benzene , toluene, xylene and other organic solvents with hydrocarbon groups.

Among two solvents having different solubility, the difference in solubility is preferably (100 μg/100 g solvent) or more (90 g/100 g solvent) or less, more preferably (1 mg/100 g solvent) or more (90 g/100 g solvent) or less. From the viewpoint of making the difference in solubility to be (100 μg/100 g solvent) or more (90 g/100 g solvent) or less, for example, in the case of performing the mixing step at room temperature (10° C. to 30° C.), it is preferable to obtain a solution in the step The solvent x used in the process is N, N-dimethylacetamide and other organic solvents with amide groups or dimethyl sulfoxide, and the solvent y used in the mixing process is organic solvents with halogenated hydrocarbon groups such as methylene chloride and chloroform. Solvents; organic solvents with hydrocarbon groups such as n-pentane, cyclohexane, n-hexane, benzene, toluene, xylene, etc.

As a method of extracting the perovskite compound from the obtained dispersion liquid containing the perovskite compound, there may be mentioned a method of recovering only the perovskite compound by performing solid-liquid separation.

Examples of the above-mentioned solid-liquid separation method include methods such as filtration, methods using solvent evaporation, and the like.

(Second embodiment of the method for producing a perovskite compound comprising A, B, and X as constituents)

The method for producing the perovskite compound may include a step of adding and dissolving component B, component X, and component A in a high-temperature solvent z to obtain a solution h, and cooling the obtained solution h. More specifically, there is a production method including the step of adding a compound containing component B and component X and a compound containing component A, or a compound containing component A and component X, into a high-temperature solvent z and dissolving them And the process of obtaining the solution h; and the process of cooling the obtained solution h.

The process of adding a compound containing B component and X component and a compound containing A component or A component and X component to a high-temperature solvent z to dissolve it to obtain a solution h may be to mix a compound containing B component and X component and a compound containing A component A step of obtaining a solution h by raising the temperature after adding the component or the compound of the component A and the component X to the solvent z.

In the above production method, the perovskite compound of the present invention can be produced by precipitating the perovskite compound of the present invention due to the difference in solubility caused by the temperature difference.

From the viewpoint of stably dispersing the perovskite compound, the above-mentioned production method preferably includes a step of adding a capping ligand. Preferably, the capped ligand is contained in solution h prior to the above-mentioned cooling step.

The above-mentioned production method preferably includes a step of removing coarse particles by methods such as centrifugation and filtration after the cooling step. The size of the coarse particles removed by the above-mentioned removal step is preferably 10 μm or more, more preferably 1 μm or more, particularly preferably 500 nm or more.

Here, the high-temperature solvent z may be any solvent at a temperature at which the compound containing the B component and the X component and the compound containing the A component or the A component and the X component dissolve, for example, it is preferably 60° C. to 600° C. The solvent is more preferably a solvent of not less than 80°C and not more than 400°C.

The cooling temperature is preferably -20°C to 50°C, more preferably -10°C to 30°C.

The cooling rate is preferably 0.1 to 1500°C/minute, more preferably 10 to 150°C/minute.

The solvent z used in the production method is not particularly limited as long as it can dissolve the compound containing component B and component X and the compound containing component A or component A and component X. For example, the solvent described as the above-mentioned (3) component can be used.

As a method of extracting the perovskite compound from the obtained dispersion liquid containing the perovskite compound, there may be mentioned a method of recovering only the perovskite compound by performing solid-liquid separation.

Examples of the above-mentioned solid-liquid separation method include methods such as filtration, methods using solvent evaporation, and the like.

[Manufacturing method of composition containing (1) component, (2) component and (3) component]

As a manufacturing method of the composition containing (1) component, (2) component, and (3) component, the following manufacturing method (a1) may be sufficient as following manufacturing method (a2), for example.

Manufacturing method (a1): The process of mixing (1) component and (3) component, and the process of mixing the mixture of (1) component and (3) component, and (2) component are included.

Manufacturing method (a2): The process of mixing (1) component and (2) component, and the process of mixing the mixture of (1) component and (2) component, and (3) component are included.

In the above-mentioned production method (a1), it is preferable to disperse (1) component in (3) component. The production method (a1) may be, for example, a production method of a composition including a step of dispersing component (1) in component (3) to obtain a dispersion, and a step of mixing the dispersion with component (2).

In embodiment, when manufacturing the composition containing the polymer of the addition polymerizable compound which has an ionic group, the following manufacturing method (a3) or manufacturing method (a4) can be employ|adopted.

Production method (a3): including the step of mixing (1) component and (3) component, the step of mixing the mixture of (1) component and (3) component with (2′) component, and the step of containing (1) component , A step in which the mixture of the component (2') and the component (3) is subjected to a polymerization treatment.

Production method (a4): including a step of mixing component (1) and component (2'), a step of mixing a mixture of component (1) and component (2') with component (3), and , A step in which the mixture of the component (2') and the component (3) is subjected to a polymerization treatment.

Here, the component (2') is a polymerizable compound having an ionic group, and is the same as the polymerizable compound having an ionic group described in the component (2).

In the mixing step included in the above production method, stirring is preferably performed from the viewpoint of improving dispersibility.

In the mixing step included in the above production method, the temperature is not particularly limited, but from the viewpoint of uniform mixing, it is preferably in the range of 0°C to 100°C, more preferably in the range of 10°C to 80°C.

From the viewpoint of improving the dispersibility of the component (1), the production method of the composition is preferably the production method (a1) or the production method (a3).

Methods for Implementing Aggregate Processing

The method of performing the polymerization treatment contained in the above-mentioned production method is not particularly limited as long as it is a method of forming a polymer by reaction in at least a part of the polymerizable functional groups contained in the addition polymerizable compound having an ionic group. limited. As a method of performing a polymerization treatment, well-known methods, such as the method of reacting with a polymerization initiator, are mentioned, for example.

As the polymerization initiator used in the method using a polymerization initiator, known polymerization initiators such as photopolymerization initiators and thermal polymerization initiators can be used.

·Photopolymerization Initiator

As an example of a photoinitiator, the photoinitiator normally used in this technical field, such as an ultraviolet type and a visible light type, is mentioned, for example.

photoradical polymerization initiator

The photoradical polymerization initiator is a polymerization initiator that generates free radicals by light such as ultraviolet light or visible light. As the photoradical polymerization initiator, as the photopolymerization initiator, for example, acetophenone, 2,2-bis Methoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 4-isopropyl-2-hydroxy-2-methylpropiophenone, 2-hydroxy-2-methylbenzene Acetone, 4,4'-bis(diethylamino)benzophenone, benzophenone, methyl (phthaloyl)benzoate, 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2-(o-benzoyl) oxime, benzoin, benzoin methyl ether, benzoin ethyl ether, Benzoin isopropyl ether, benzoin isobutyl ether, benzoin octyl ether, benzyl dimethyl ketal, benzyl diethyl ketal, diacetyl and other carbonyl compounds, formazan Anthraquinone, chloranthraquinone, chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone and other anthraquinone or thioxanthone derivatives, diphenyl disulfide, dithioamino Sulfur compounds such as formate.

·Photocationic polymerization initiator

As the cationic polymerization initiator, any well-known initiator that generates an acid by irradiation with active energy rays can be used without particular limitation, and examples thereof include sulfonium salts, iodonium salts, phosphonium salts, and pyridinium salts.

For example, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, bis(4-(diphenylsulfonium)-phenyl)sulfide-bis(hexafluorophosphate), bis (4-(Diphenylsulfonyl)-phenyl)sulfide-bis(hexafluoroantimonate), 4-bis(p-tolyl)sulfonyl-4'-tert-butylphenylcarbonyl-diphenyl Sulfonium-hexafluoroantimonate, 7-bis(p-tolyl)sulfonium-2-isopropylthioxanthone hexafluorophosphate, 7-bis(p-tolyl)sulfonium-2-iso Propylthioxanthone hexafluoroantimonate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, bis(dodecylphenyl)iodonium tetrakis(pentafluorophenyl) Borate, tetrafluorophosphonium hexafluorophosphate, tetrafluorophosphonium hexafluoroantimonate.

thermal free radical polymerization initiator

The thermal radical polymerization initiator is a polymerization initiator that generates radicals by heat, and examples thereof include 2,2'-azobisisobutyronitrile, 2,2'-azobisisovaleronitrile, 2,2' -Azobis(2,4-dimethylvaleronitrile), 4,4'-azobis(4-cyanovaleric acid), 1,1'-azobis(cyclohexanecarbonitrile), 2 , 2'-azobis(2-methylpropane), 2,2'-azobis(2-methylpropionamidine) 2 hydrochloride and other azo compounds, methyl ethyl ketone peroxide, peroxide Ketone peroxides such as methyl isobutyl ketone oxide, cyclohexanone peroxide, acetylacetone peroxide, isobutyl peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide Diacyl peroxides such as o-toluyl peroxide, lauroyl peroxide, p-chlorobenzoyl peroxide, 2,4,4-trimethylpentyl-2-peroxide Hydrogen peroxides such as hydrogen, dicumyl peroxide, cumene hydroperoxide, tert-butyl peroxide; dicumyl peroxide, tert-butyl cumyl peroxide, di-tert-butyl peroxide, tri (tert-butyloxy)triazine and other dialkyl peroxides; 1,1-di-tert-butylperoxycyclohexane, 2,2-bis(tert-butylperoxy)butane Ketones; tert-butyl peroxypivalate, tert-butyl peroxy(2-ethylhexanoate), tert-butyl peroxyisobutyrate, di-tert-butyl peroxyhexahydroterephthalate, peroxy Di-tert-butyl azelate, tert-butyl peroxy-3,5,5-trimethylhexanoate, tert-butyl peroxyacetate, tert-butyl peroxybenzoate, di-tert-butyl peroxytrimethyl adipate Alkyl peresters such as tert-butyl ester, percarbonate such as diisopropyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, tert-butyl peroxyisopropyl carbonate, etc., can also be 2, 2'-Azobisisobutyronitrile.

These polymerization initiators may be used alone or in combination of two or more.

These polymerization initiators can be suitably selected and used according to the kind and ratio of the addition polymerizable compound which has an ionic group to be used.

The amount of the polymerization initiator used is preferably 0.001 to 90% by mass, more preferably 0.1 to 80% by mass, and further Preferably it is 1-60 mass %.

In the case of performing the polymerization treatment, for example, the composition may be left to stand or stirred at a temperature described later for a certain period of time.

·Photopolymerization treatment

In order to initiate the photopolymerization reaction, the composition containing the addition polymerizable compound having an ionic group and the photopolymerization initiator may be irradiated with light of an appropriate wavelength capable of generating radicals or ions from the photopolymerization initiator. The intensity of the light to be irradiated is not particularly limited, and may be, for example, not less than 0.5 W/m ² and not more than 500 W/m ² .

The type of light to be irradiated is not particularly selected as long as radicals or ions can be generated from the photopolymerization initiator. Visible light, ultraviolet rays, near infrared rays, etc. are mentioned. Examples of lamps for generating these light rays include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, xenon lamps, ultraviolet LEDs, blue LEDs, white LEDs, H lamps, D lamps, and V lamps manufactured by Melting Corporation. Lamp, carbon arc, tungsten lamp, fluorescent lamp, helium cadmium laser, argon laser, Nd:YAG laser, carbon dioxide laser, titanium sapphire laser, excimer laser, etc. Sunlight can also be used.

The irradiation time and irradiation intensity can be appropriately set according to the wavelength of the light source, the type of the addition polymerizable compound having an ionic group, the properties of the target polymer, and the like.

The temperature in the photopolymerization treatment may be sufficient as long as the polymerization proceeds sufficiently, for example, it is preferably from 5°C to 150°C, more preferably from 10°C to 100°C, even more preferably from 15°C to 80°C.

The time required for the photopolymerization treatment may be sufficient as long as the polymerization proceeds, for example, from 10 seconds to 1 week, preferably from 30 seconds to 1 day, more preferably from 1 minute to 1 hour.

The atmosphere in the photopolymerization treatment is not particularly limited, but it is preferably replaced with an inert gas such as nitrogen or argon from the viewpoint of improving reactivity.

From the viewpoint of improving the dispersibility of the addition polymerizable compound having an ionic group contained in the composition, stirring is preferably performed.

thermal polymerization treatment

In order to carry out the thermal polymerization reaction, it is preferable to heat a composition containing an addition polymerizable compound having an ionic group and a thermal polymerization initiator at an appropriate temperature at which radicals or ions can be generated from the thermal polymerization initiator.

The temperature in the polymerization treatment may be sufficient as long as the polymerization proceeds sufficiently. For example, it is preferably 5°C to 200°C, more preferably 10°C to 150°C, and still more preferably 15°C to 100°C.

The time required for the polymerization treatment is sufficient as long as the polymerization is sufficiently advanced, for example, it is 1 minute to 1 week, preferably 10 minutes to 5 days, more preferably 30 minutes to 3 days.

The atmosphere in the polymerization treatment is not particularly limited, but it is preferably replaced with an inert gas such as nitrogen or argon from the viewpoint of improving reactivity.

From the viewpoint of increasing the addition polymerizable compound having an ionic group contained in the composition, stirring is preferably performed.

In this embodiment, (2) component and (3) component can be mixed in any process contained in the manufacturing method of the said (1) component. For example, it may be the following production method (a5) or the following production method (a6).

Production method (a5): comprising a step of dissolving a compound containing component B and component X, a compound containing component A or component A and component X, and component (2) in component (3) to obtain a solution g; and obtaining The process of mixing the solution g and the solvent y whose solubility in the solvent of the perovskite compound is lower than that of the component (3) used in the process of obtaining the solution.

Production method (a6): comprising adding and dissolving a compound containing component B and component X, a compound containing component A or component A and component X, and component (2) to component (3) at high temperature to obtain a solution h process; and a process of cooling the obtained solution h.

In this embodiment, when producing the composition containing the polymer of the addition polymerizable compound which has an ionic group, the following production method (a7) or the following production method (a8) can be used.

Production method (a7): comprising the steps of dissolving a compound containing component B and component X, a compound containing component A or component A and component X, and component (2′) in component (3) to obtain a solution g; and A step of mixing the obtained solution g with a solvent y whose solubility in the solvent of the perovskite compound is lower than that of the (3) component used in the step of obtaining the solution; and for (1) component, (2′) component and (3 ) The process of subjecting the mixture of components to polymerization treatment.

Production method (a8): including adding a compound containing component B and component X, a compound containing component A or component A and component X, and component (2') to component (3) at high temperature and dissolving it to obtain a solution h and a step of cooling the obtained solution h; and a step of subjecting the cooled solution h containing (1) component, (2′) component and (3) component to a polymerization treatment.

The conditions of each step included in these production methods are the same as those described in the first and second embodiments of the above-mentioned production method of the perovskite compound.

[Manufacturing method of composition containing (1) component, (2) component, (3) component and (5) component]

For example, the production method of the composition containing (1) component, (2) component, (3) component and (5) component, except mixing Other than (5) component, the method similar to the manufacturing method of the composition containing (1) component, (2) component, and (3) component can be employ|adopted.

In the present embodiment, from the viewpoint of improving the dispersibility of the component (1), the component (5) is preferably prepared in the method for producing a perovskite compound having A, B, and X as components of the component (1). Mixed in any process included. For example, it is preferably produced by the following production method (b1), production method (b2), production method (b3) or production method (b4).

Production method (b1): comprising dissolving a compound containing component B and component X, a compound containing component A or component A and component X, component (2) and component (5) in component (3) to obtain a solution g a step; and a step of mixing the obtained solution g with a solvent y having a lower solubility of the perovskite compound in the solvent than the component (3) used in the step of obtaining the solution.

Production method (b2): Including adding a compound containing component B and component X, a compound containing component A or component A and component X, component (2) and component (5) to component (3) at high temperature and dissolving it , a step of obtaining a solution h; and a step of cooling the obtained solution h.

Production method (b3): comprising dissolving a compound containing component B and component X, a compound containing component A or component A and component X, component (2') and component (5) in component (3) to obtain a solution g the process; and the process of mixing the obtained solution g with the solvent y having a lower solubility in the solvent than the (3) component used in the process of obtaining the solution; and (1) component, (2' ) component, a mixture of (3) component and (5) component is subjected to a polymerization treatment.

Production method (b4): including adding a compound containing component B and component X, a compound containing component A or component A and component X, component (2′) and component (5) to component (3) at high temperature and making it A step of dissolving to obtain a solution h; and a step of cooling the obtained solution h; and performing a polymerization treatment on the cooled solution h containing (1) component, (2′) component, (3) component, and (5) component process.

[Manufacturing method of composition containing (1) component, (2) component and (4) component]

As a manufacturing method of the composition containing (1) component, (2) component, and (4) component, the method of mixing (1) component, (2) component, and (4) component is mentioned.

It is preferable to carry out the process of mixing (1) component, (2) component, and (4) component, stirring, from a viewpoint of improving the dispersibility of (1) component.

In the step of mixing component (1), component (2), and component (4), the temperature is not particularly limited, but from the viewpoint of uniform mixing, it is preferably in the range of 0°C to 100°C, more preferably 10°C or higher range below 80°C.

As a manufacturing method of the composition containing (1) component, (2) component, and (4) component, following manufacturing method (c1), (c2), (c3) is mentioned, for example.

Production method (c1): a step of dispersing (1) component in (4) component to obtain a dispersion; and a step of mixing the obtained dispersion and (2) component.

Production method (c2): including the step of dispersing (2) component in (4) component to obtain a dispersion; and the step of mixing the obtained dispersion and (1) component.

Manufacturing method (c3): includes the process of dispersing the mixture of (1) component and (2) component in (4) component.

Among the production methods of (c1) to (c3), the production method of (c1) is preferable from the viewpoint of improving the dispersibility of the component (1). The composition of the present invention can be obtained as a mixture of a dispersion in which (1) component is dispersed in (4) component and (2) component by the above method.

In the step of obtaining each dispersion contained in the production methods of (c1) to (c3), component (4) may be added dropwise to either or both of component (1) and component (2), or Either or both of (1) component and (2) component are dripped at (4) component.

From the viewpoint of improving dispersibility, it is preferable to dropwise add either or both of (1) component and (2) component to (4) component.

In each mixing step included in the production methods of (c1) to (c3), component (1) or component (2) may be added dropwise to the dispersion, or the dispersion may be added dropwise to component (1) or (2).

From the viewpoint of improving dispersibility, it is preferable to add (1) component or (2) component dropwise to the dispersion.

As (4) component, when a polymer is used, the polymer may be a polymer dissolved in a solvent.

The solvent in which the polymer is dissolved is not particularly limited as long as it can dissolve the polymer (resin), but is preferably a solvent that hardly dissolves the component (1) used in the present invention.

As a solvent in which the above-mentioned polymer is dissolved, for example, the solvent described as the above-mentioned (3) component can be used.

Moreover, the manufacturing method of the composition containing (1) component, (2) component, and (4) component may be following manufacturing method (c4) or manufacturing method (c5).

Production method (c4): comprising the steps of dispersing component (1) in component (3) to obtain a dispersion liquid; mixing the obtained dispersion liquid with component (4) to obtain a mixed liquid; The process of mixing the mixed solution with the (2) component.

The production method (c5) may also include a step of dispersing the component (1) in the component (3) to obtain a dispersion liquid; a step of mixing the dispersion liquid with the component (2′) to obtain a mixed liquid; a step of polymerizing to obtain a liquid mixture containing a polymer of an addition polymerizable compound having an ionic group; and a step of mixing the liquid mixture containing a polymer with the component (4).

[Manufacturing method of composition containing (1) component, (2) component, (4) component and (5) component]

The manufacturing method of the composition containing (1) component, (2) component, (4) component, and (5) component can adopt the same as already explained containing (1) component, (2) component except adding (5) component. Component is the same method as the production method of the composition of (4) component.

(5) The component may be added in any process contained in the production method of the perovskite compound having A, B and X of the above-mentioned (1) component as constituent components, or may be added in any process containing the above-mentioned (1) component, ( 2) Add in any process included in the manufacturing method of the composition of a component and (4).

From the viewpoint of improving the dispersibility of the component (1), the component (5) is preferably added in any of the steps included in the production method of the perovskite compound composed of components A, B, and X of the component (1). .

In the manufacturing method of the composition containing (1) component, (2) component, (4) component and (5) component, can use (3) component solvent, thus, for example, can be used as at least a part by (5) Ingredient-coated (1) component dispersed in (3) component dispersion, and (2) component dispersed in (3) component dispersion, and (4) component mixture, or at least a part is wrapped by (5) component The coating (1) component and (2) component are disperse|distributed in the dispersion of (3) component, and the mixture of (4) component, and the composition of this embodiment is obtained.

[combination containing (1) component, (2) component and (4') component, and the total content ratio of (1) component, (2) component and (4') component with respect to the total mass of the composition is 90% by mass or more manufacturing method]

As containing (1) component, (2) component and (4') component, and the total content ratio of (1) component, (2) component and (4') component with respect to the total mass of a composition is 90 mass % or more The production method of the composition, for example, the following production method (Y) can be mentioned.

Production method (Y): a production method comprising the steps of mixing (1) component, (2) component, and a polymerizable compound, and the step of polymerizing the polymerizable compound, and comprising mixing (1) component, (2) component, and A production method of a step of mixing polymers dissolved in a solvent, and a step of removing the solvent.

In the mixing process included in the above-mentioned production method, the same mixing method as the production method of the composition containing (1) component, (2) component, and (4) component described above can be used.

Examples of the above-mentioned production method include the following production methods (d1) to (d6).

Production method (d1): comprising the steps of dispersing the component (1) in a polymerizable compound to obtain a dispersion; mixing the obtained dispersion with (2); and polymerizing the polymerizable compound.

The production method (d2): comprises a step of dispersing the component (1) in a polymer dissolved in a solvent to obtain a dispersion; a step of mixing the obtained dispersion with the component (2); and a step of removing the solvent.

Production method (d3): comprising a step of dispersing component (2) in a polymerizable compound to obtain a dispersion; a step of mixing the obtained dispersion with component (1); and a step of polymerizing the polymerizable compound .

The production method (d4): comprises a step of dispersing the component (2) in a polymer dissolved in a solvent to obtain a dispersion; a step of mixing the obtained dispersion with the component (1); and a step of removing the solvent.

Production method (d5): includes a step of dispersing a mixture of component (1) and component (2) in a polymerizable compound, and a step of polymerizing the polymerizable compound.

Production method (d6): includes a step of dispersing a mixture of component (1) and component (2) in a polymer dissolved in a solvent, and a step of removing the solvent.

The step of removing the solvent included in the above-mentioned production method may be a step of standing at room temperature to allow natural drying, or may be a step of evaporating the solvent by drying under reduced pressure using a vacuum dryer or heating.

For example, the solvent can be removed by drying at 0°C to 300°C for 1 minute to 7 days.

The step of polymerizing the polymerizable compound included in the above production method can be performed by appropriately using known polymerization reactions such as radical polymerization.

For example, in the case of radical polymerization, by adding a radical polymerization initiator to a mixture of (1) component, (2) component, and a polymerizable compound, a radical is generated and a polymerization reaction can be performed.

The radical polymerization initiator is not particularly limited, and examples thereof include photoradical polymerization initiators and the like.

As said radical photopolymerization initiator, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide etc. are mentioned, for example.

[Containing (1) component, (2) component, (4') component and (5) component, relative to the total mass of the composition, (1) component, (2) component, (4') component and (5) Production method of composition whose total content ratio of components is 90% by mass or more]

Contains (1) component, (2) component, (4') component and (5) component, relative to the total mass of the composition, (1) component, (2) component, (4') component and (5) component The production method of the composition whose total content ratio is 90% by mass or more, for example, in addition to containing (1) component, (2) component and (4′) component, with respect to the total mass of the composition, (1) component, (2) Ingredient (2) and (4') component total content rate is 90% by mass or more of the production method of the composition contained in any process included in (5) component, the rest may be the same as already described containing (1) Manufacture of a composition in which the total content ratio of component (1), component (2) and component (4') is 90% by mass or more with respect to the total mass of the composition The method is the same.

From the viewpoint of improving the dispersibility of the perovskite compound, the component (5) is preferably added in any of the following steps included in the method for producing a perovskite compound comprising A, B and X as constituents in (1) .

- Any one of the steps included in the production method of the above-mentioned perovskite compound.

- A step of mixing the above (1) and (2) with a polymerizable compound.

- A step of mixing the above (1) and (2) with a polymer dissolved in a solvent.

[Manufacturing method of composition containing (6) component]

The manufacturing method of the composition containing (6) component can employ|adopt the method similar to the manufacturing method of the said composition except having mixed (6) component further. Before mixing component (1) and component (2), it is preferable to mix component (1) and component (6), for example, the following production method (a1-1) can be used, or the following production method (a2-1) can be used .

Production method (a1-1): comprising a step of mixing component (1) and (3), a step of mixing a mixture of component (1) and (3) with component (6), and mixing component (2) with (1) The process of mixing the mixture of components (3) and (6).

Production method (a2-1): including a step of mixing (1) component and (6), a step of mixing a mixture of (1) component and (6) with (2) component, and mixing (1) component, ( A step of mixing the mixture of 2) and (6) with the component (3).

[mixing process with (1)-1 component)]

In the manufacturing method of the composition of this embodiment mentioned above, you may have the process of mixing the said (1)-1 component further. This step can be prepared by preparing a dispersion liquid containing a perovskite compound having a different emission peak wavelength from that of the component (1) and a solvent, and the above-mentioned dispersion liquid is composed of the components (1) and (2) as essential components, and contains other optional components. The mixed solution is mixed to implement. In this step, as (1)-1 component, a liquid mixture containing (1)-1 component, (2) component as an optional component, and the above-mentioned other optional components can be used. The mixed solution containing (1)-1 component and (2) component as an optional component and the above-mentioned other optional components can be composed of (1) component and (2) component as already described, and can be used for other optional components. The mixture is made in the same way.

"Determination of Perovskite Compounds"

The amount of the perovskite compound contained in the composition of the present invention is measured using an inductively coupled plasma mass spectrometer ICP-MS (for example, ELANDRC II manufactured by PerkinElmer) and an ion chromatograph (for example, Integrion manufactured by Thermo Fischer Scientific).

Measurement is performed after dissolving the perovskite compound in a good solvent such as N,N-dimethylformamide.

"Determination of Luminescence Spectrum"

The emission spectrum of the composition of the present invention is measured using an absolute PL quantum yield measuring device (for example, Hamamatsu Photonics Co., Ltd., C9920-02) under excitation light of 450 nm at room temperature and in the atmosphere.

In the composition containing (1) component, (2) component, and (3) component, the concentration of the perovskite compound contained in the composition was adjusted to 200 ppm (μg/g), and the emission spectrum was measured.

The mixing ratio of the composition containing (1), (2) and (4) was adjusted so that the concentration of the perovskite compound contained in the composition was 2000 ppm (μg/g), and the emission spectrum was measured. The same applies when replacing the component (4) with the component (4').

"Evaluation of luminescence peaks when two types of perovskite compounds are mixed 1"

A perovskite compound (perovskite compound 2) having a light emission peak wavelength different from that of the above-mentioned perovskite compound was mixed with 1 mL of the dispersion composition of the present invention containing a perovskite compound (perovskite compound 1). The emission spectrum was measured before and after the mixing of the two perovskite compounds, and as an evaluation index of the emission spectrum, (the emission peak wavelength (nm) of the perovskite compound 1 before mixing)-(the emission of the perovskite compound 1 after mixing The absolute value of the peak wavelength (nm)), and the absolute value of (the emission peak wavelength (nm) of the perovskite compound 2 before mixing)-(the emission peak wavelength (nm) of the perovskite compound 2 after mixing), and the number of peaks.

"Evaluation of luminescence peaks when two types of perovskite compounds are mixed 2"

In the composition of the present invention containing a perovskite compound (perovskite compound 1), a perovskite compound (perovskite compound 2) having a light emission peak wavelength different from that of the above-mentioned perovskite compound is mixed, and after forming a film, cutting The thickness is 100 μm, 1 cm×1 cm. The emission spectrum was measured before and after the mixing of the two perovskite compounds, and as an evaluation index of the emission spectrum, (the emission peak wavelength (nm) of the perovskite compound 1 before mixing)-(the emission of the perovskite compound 1 after mixing The absolute value of the peak wavelength (nm)), and the absolute value of (the emission peak wavelength (nm) of the perovskite compound 2 before mixing)−(the emission peak wavelength (nm) of the perovskite compound 2 after mixing), and the number of peaks.

In the composition of the embodiment, the evaluation of the luminescence peaks when the two perovskite compounds are mixed by the above-mentioned measuring method may be 23 nm or less, 20 nm or less, or 15 nm or less, and the number of peaks may be 2.

As one aspect of the present invention, the evaluation of the luminescence peaks when the two perovskite compounds are mixed by the above measurement method is preferably 0 nm to 23 nm, more preferably 0 nm to 20 nm, and even more preferably 0 nm to 15 nm.

The luminescence peaks when the two perovskite compounds are mixed as measured by the above measurement method are not particularly limited. For example, for the two confirmed luminescence peak wavelengths, the absolute value of the difference in wavelength is preferably 30 nm or more, more preferably 50 nm or more, and further Preferably it is 100 nm or more. In addition, the minimum luminous intensity in the wavelength region between the two luminous peaks is preferably 80% or less of the luminous intensity of the higher of the two luminous peak wavelengths, more preferably 50% or less, even more preferably 30% or less .

<film>

The film of the present invention is a composition containing (1) component, (2) component and (4') component, and the total content ratio of (1) component, (2) component and (4') component is used relative to the composition The total mass of the film is more than 90% by mass of the composition. The composition may contain (5) component.

The shape of the film is not particularly limited, and may be any shape such as a sheet shape or a rod shape. In this specification, "rod-like shape" means, for example, a shape having anisotropy. As the anisotropic shape, a plate-like shape in which the length of each side is different is exemplified.

The thickness of the film may be from 0.01 μm to 1000 mm, from 0.1 μm to 10 mm, or from 1 μm to 1 mm.

In this specification, the thickness of the said film can be obtained by measuring at arbitrary 3 points with a micrometer, and calculating the average value.

The film can be single layer or multilayer. In the case of multiple layers, the same type of composition of the embodiment may be used for each layer, or the compositions of mutually different types of embodiments may be used.

The film can be formed on a substrate by, for example, the production methods of the production methods (i) to (iV) of the laminated structure described later. In addition, the film can be obtained by peeling off the substrate.

<Layered structure>

The laminated structure of the present invention has multiple layers, at least one layer of which is the above-mentioned film.

Among the plurality of layers included in the laminated structure, optional layers such as substrates, barrier layers, and light-scattering layers can be exemplified as layers other than the above-mentioned films.

The shape of the laminated film is not particularly limited, and may be any shape such as a sheet shape or a rod shape.

(substrate)

The layers that the laminated structure of the present invention may have are not particularly limited, and examples thereof include substrates.

The substrate is not particularly limited, and may be a film, but a transparent substrate is preferable from the viewpoint of extracting emitted light. As the substrate, known organic materials such as polymers such as polyethylene terephthalate and glass can be used, for example.

For example, in a laminated structure, the above-mentioned film may be provided on a substrate.

FIG. 1 is a cross-sectional view schematically showing the structure of a laminated structure according to the present embodiment. In the first multilayer structure 1 a , the film 10 of the present embodiment is provided between the first substrate 20 and the second substrate 21 . The membrane 10 is sealed by a sealing layer 22 .

One aspect of the present invention is a laminated structure 1a having a first substrate 20, a second substrate 21, the film 10 of the present embodiment located between the first substrate 20 and the second substrate 21, and a sealant. layer 22 , wherein the sealing layer is disposed on a surface of the film 10 that is not in contact with the first substrate 20 and the second substrate 21 .

(barrier layer)

The layers that the laminated structure of the present invention may have are not particularly limited, and examples include barrier layers. From the viewpoint of protecting the above-mentioned composition from water vapor in the outside air and air in the atmosphere, a barrier layer may be included.

The barrier layer is not particularly limited, but is preferably a transparent barrier layer from the viewpoint of extracting emitted light. As the barrier layer, known barrier layers such as polymers such as polyethylene terephthalate and glass films can be used, for example.

(light scattering layer)

The layer that the laminated structure of the present invention may have is not particularly limited, and a light-scattering layer may be mentioned. From the viewpoint of effectively utilizing incident light, a light scattering layer may also be included.

The light scattering layer is not particularly limited, but is preferably a transparent layer from the viewpoint of extracting emitted light. As the light-scattering layer, known light-scattering layers such as light-scattering particles such as silica particles and reinforced diffusion films can be used.

<light emitting device>

The light-emitting device of the present invention can be obtained by combining the composition or laminated structure according to the embodiment of the present invention with a light source. A light-emitting device is a device that emits light from a composition or a laminated structure provided at a subsequent stage by irradiating light emitted from a light source to the composition or a laminated structure and extracts the light. Among the layers included in the laminated structure in the light-emitting device, examples of layers other than the above-mentioned film, substrate, barrier layer, and light-scattering layer include a light reflection member, a brightness enhancement portion, a prism sheet, a light guide plate, Arbitrary layers such as dielectric material layers between elements.

One aspect of the present invention is a light-emitting device 2 in which a prism sheet 50 , a light guide plate 60 , the above-mentioned first laminated structure 1 a , and a light source 30 are laminated in this order.

(light source)

The light source constituting the light-emitting device of the present invention is not particularly limited, but a light source having an emission wavelength of 600 nm or less is preferable from the viewpoint of emitting light from the component (1) in the composition or laminated structure. As a light source, well-known light sources, such as a light emitting diode (LED) such as a blue light emitting diode, a laser, and EL, can be used, for example.

(light reflection part)

There are no particular limitations on the layers that may be included in the laminated structure constituting the light-emitting device of the present invention, and light-reflecting members may be mentioned. From the viewpoint of irradiating light from a light source to the above composition or laminated structure, a light reflection member may be included. The light reflection member is not particularly limited, but may also be a reflective film.

As the reflective film, known reflective films such as reflective mirrors, reflective particle films, reflective metal films, or reflectors can be used, for example.

(brightness enhancement part)

There are no particular limitations on the layers that may be included in the laminated structure constituting the light-emitting device of the present invention, and examples thereof include a luminance enhancement portion. From the viewpoint of reflecting and returning part of the light toward the direction in which the light is transmitted, a brightness enhancement unit may be included.

(prism sheet)

The layer that may be included in the laminated structure constituting the light-emitting device of the present invention is not particularly limited, and a prism sheet may be mentioned. A prism sheet typically has a base part and a prism part. In addition, the base part may be omitted depending on adjacent members. The prism sheet can be bonded to an adjacent member via any appropriate adhesive layer (for example, an adhesive layer, an adhesive layer). The prism sheet is configured by juxtaposing a plurality of unit prisms protruding toward the side (back side) opposite to the viewing side. By arranging the convex portion of the prism sheet toward the back side, the light transmitted through the prism sheet can be easily focused. In addition, if the convex portion of the prism sheet is arranged toward the back side, compared with the case where the convex portion is arranged toward the viewing side, less light is reflected without incident on the prism sheet, and a display with high brightness can be obtained.

(light guide plate)

The layers that may be included in the laminated structure constituting the light-emitting device of the present invention are not particularly limited, and examples include light guide plates. As the light guide plate, for example, any suitable light guide plate such as a light guide plate formed with a lens pattern on the back side, a light guide plate formed with a prism shape, etc. direction deflection.

(dielectric material layer between elements)

The layers that can be included in the laminated structure constituting the light-emitting device of the present invention are not particularly limited, and include layers made of one or more dielectric materials on the optical path between adjacent elements (layers) (inter-element medium). material layer).

There is no particular limitation on one or more media contained in the dielectric material layer between elements, including vacuum, air, gas, optical material, adhesive, optical adhesive, glass, polymer, solid, liquid, gel , curing materials, optical bonding materials, index matching or mismatching materials, gradient index materials, cladding or anti-cladding materials, spacers, silicone, brightness enhancing materials, scattering or diffusing materials, reflective or antireflective materials , wavelength selective material, wavelength selective anti-reflection material, color filter, or a suitable medium known in the above technical field.

Specific examples of the light-emitting device of the present invention include, for example, a light-emitting device provided with a wavelength conversion material for an EL display or a liquid crystal display.

Specifically, (E1) put the composition of the present invention in a glass tube or the like and seal it, and place it on a blue light-emitting diode as a light source and a light guide plate along the end surface (side surface) of the light guide plate. Among them, a backlight that converts blue light into green or red light (edge type backlight).

In addition, (E2) the composition of the present invention is formed into a sheet, a film sandwiched and sealed between two barrier films is placed on a light guide plate, and the blue film placed on the end surface (side surface) of the light guide plate is placed on the light guide plate. A backlight (surface-mounted backlight) in which the blue light irradiated by a color light-emitting diode on the above-mentioned sheet through the light guide plate is converted into green light or red light.

Also enumerated (E3) the composition of the present invention is dispersed in resin etc., is arranged near the light-emitting part of blue light-emitting diode, the backlight (chip encapsulation type (on -chip) backlight).

(E4) A backlight in which the composition of the present invention is dispersed in a resist and placed on a color filter to convert blue light irradiated from a light source into green light or red light is also mentioned.

In addition, as a specific example of the light-emitting device according to the present invention, it is possible to mold the composition according to the embodiment of the present invention, arrange it in the rear stage of a blue light-emitting diode as a light source, and convert blue light into green light or red light. Light that emits white light.

<monitor>

As shown in FIG. 2 , the display 3 of this embodiment includes a liquid crystal panel 40 and the above-mentioned light emitting device 2 in this order from the viewing side. A light emitting device (2) includes a second laminated structure (1b) and a light source (30). The second laminated structure 1 b is a laminated structure in which the first laminated structure 1 a further includes a prism sheet 50 and a light guide plate 60 . The display may also have any suitable other components.

One aspect of the present invention is a liquid crystal display 3 in which a liquid crystal panel 40 , a prism sheet 50 , a light guide plate 60 , the above-mentioned first laminated structure 1 a , and a light source 30 are sequentially laminated.

(LCD panel)

The liquid crystal panel typically includes a liquid crystal cell, a viewing-side polarizing plate disposed on the viewing side of the liquid crystal cell, and a rear-side polarizing plate disposed on the rear side of the liquid crystal cell. The viewing-side polarizing plate and the back-side polarizing plate can be arranged so that their respective absorption axes are substantially perpendicular or parallel.

(LCD unit)

A liquid crystal cell has a pair of substrates and a liquid crystal layer as a display medium sandwiched between the substrates. In a general structure, a color filter and a black matrix are arranged on one substrate, and a switching element for controlling the electro-optical characteristics of liquid crystal, a scanning line for supplying a gate signal to the switching element, and a source electrode are arranged on the other substrate. Signal lines, pixel electrodes and counter electrodes for signals. The distance between the above-mentioned substrates (cell gap) can be controlled by spacers or the like. On the side of the substrate that is in contact with the liquid crystal layer, for example, an alignment film made of polyimide or the like may be provided.

(Polarizing plate)

A polarizing plate typically has a polarizing plate and protective layers arranged on both sides of the polarizing plate. The polarizing plate is typically an absorbing polarizing plate.

Any appropriate polarizing plate can be used as the above-mentioned polarizing plate. For example, adsorption of iodine or a dichroic dye on a hydrophilic polymer film such as a polyvinyl alcohol film, a partially formalized polyvinyl alcohol film, or an ethylene-vinyl acetate copolymer partially saponified film can be mentioned. Polyethylene-based oriented films such as films obtained by uniaxially stretching chromatic substances, polyvinyl alcohol dehydration-treated products, or polyvinyl chloride dehydrochloric acid-treated products. Among them, a polarizing plate obtained by adsorbing a dichroic substance such as iodine on a polyvinyl alcohol-based film and uniaxially stretching it is particularly preferable because of its high polarizing dichroism ratio.

Examples of uses of the composition of the present invention include wavelength conversion materials for light-emitting diodes (LEDs).

<LED>

The composition of the present invention can be used, for example, as a material for a light-emitting layer of an LED.

As an LED containing the composition of the present invention, for example, a method in which the composition of the present invention and conductive particles such as ZnS are mixed, laminated in a film form, an n-type transport layer is laminated on one side, and a p-type transport layer is laminated on the other side. When a current is passed through the layer, the holes of the p-type semiconductor and the electrons of the n-type semiconductor cancel the charges in the particles of the (1) component and (2) component contained in the composition of the joint surface to emit light.

<solar battery>

The composition of the present invention can be used as an electron-transporting material contained in an active layer of a solar cell.

As the above-mentioned solar cell, the constitution is not particularly limited, and examples include, in this order, a fluorine-doped tin oxide (FTO) substrate, a dense layer of titanium oxide, a porous alumina layer, an active layer containing the composition of the present invention, 2, 2',7,7'-Tetrakis[N,N-bis(4-methoxyphenyl)amino]-9,9'-spirobifluorene (Spiro-MeOTAD) and other hole transport layers, and silver (Ag ) electrode solar cell.

The dense layer of titanium oxide has the function of electron transport, the effect of suppressing the roughness of FTO, and the function of suppressing reverse electron movement.

The porous alumina layer has a function of improving light absorption efficiency.

The composition of the present invention contained in the active layer has the functions of charge separation and electron transport.

<Manufacturing method of laminated structure>

Examples of the method for producing the laminated structure include the following production methods (i), (ii), (iii), and (iv).

Production method (i): includes a step of mixing component (1), component (2), component (3) and component (4'), a step of applying the obtained mixture on a substrate, and a step of removing the solvent.

Production method (ii): includes a step of mixing component (1), component (2) and a polymer dissolved in a solvent, a step of applying the obtained mixture on a substrate, and a step of removing the solvent.

The production method (iii): comprises mixing the composition containing (1) component, (2) component and (4′) component, that is, (1) component, (2) component and (4′) component with respect to the total amount of the composition A step of attaching the composition whose total content by mass is 90% by mass or more to the substrate.

Production method (iv): includes a step of mixing component (1), component (2) and a polymerizable compound, a step of applying the obtained mixture on a substrate, and a step of polymerizing the polymerizable compound.

In the step of mixing and the step of removing the solvent contained in the production method of (i) above, the step of mixing and the step of removing the solvent contained in the production method of (ii) above, in the production method of (iv) above The step of mixing and the step of polymerizing the polymerizable compound may be the same as the steps included in the production method of the composition containing (1) component, (2) component, and (4′) component, respectively. The process in which the total content ratio of (1) component, (2) component, and (4') component with respect to the total mass of a composition is 90 mass % or more.

There are no particular limitations on the steps of coating on the substrate included in the production methods of (i), (ii) and (iv), and gravure coating, bar coating, printing, spray coating, and spin coating can be used. , dipping method, die coating method and other known coating and coating methods.

In the step of bonding to the substrate included in the production method of (iii), any adhesive can be used.

The adhesive is not particularly limited as long as it does not dissolve the compounds of the (1) component and (2) component, and known adhesives can be used.

The method for producing a laminated structure may include a step of bonding an arbitrary film to the laminated structure obtained in (i) to (iv).

Examples of optional films to be bonded include reflective films and diffusion films.

In the step of laminating the film, any adhesive can be used.

The above-mentioned adhesive is not particularly limited as long as it does not dissolve the compounds of (1) component and (2) component, and known adhesives can be used.

<Manufacturing method of light-emitting device>

For example, there may be mentioned a production method including the step of providing the above-mentioned light source and the step of providing the above-mentioned composition or laminated structure on an optical path at a subsequent stage from the light source.

In addition, the technical scope of the present invention is not limited to the above-mentioned embodiments, and various changes can be made within the scope not departing from the gist of the present invention.

Example

Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example.

(Concentration measurement of perovskite compound)

The concentration of the perovskite compound in the compositions obtained in Examples 1 to 18 and Comparative Examples 1 to 3 was measured by the following method.

To the dispersion liquid containing the perovskite compound and the solvent obtained by redispersion, N,N-dimethylformamide is added, thereby dissolving the perovskite compound.

Then, measurement was performed using ICP-MS (ELAN DRCII, manufactured by PerkinElmer) and an ion chromatograph (Integrion, manufactured by Thermo Fischer Scientific).

(Measurement of Luminescence Spectrum)

The emission spectra of the compositions obtained in Examples 1 to 18 and Comparative Examples 1 to 3 were measured using an absolute PL quantum yield measuring device (manufactured by Hamamatsu Photonics Co., Ltd., C9920-02) with an excitation light of 450 nm, room temperature, and the atmosphere.

(Evaluation of luminescence peaks when two types of perovskite compounds are mixed)

Different perovskite compounds were added to 1 mL of the dispersion compositions obtained in Examples 1 to 18 and Comparative Examples 1 to 3, and adjusted to 200 ppm (μg/g) each with n-hexane. The emission spectrum was measured before and after the mixing of the two perovskite compounds, and as an evaluation index of the emission spectrum, (the emission peak (nm) of the perovskite compound 1 before mixing)-(the emission peak of the perovskite compound 1 after mixing The absolute value of peak (nm)), and the absolute value of (luminescence peak (nm) of perovskite compound 2 before mixing)-(luminescence peak of perovskite compound 2 after mixing (nm)), and the absolute value of peak quantity.

(Observation with a scanning electron microscope)

The compositions obtained in Example 14 and Example 18 were observed using a scanning electron microscope (manufactured by JEOL Ltd., JEM-5500). The powder that dried naturally at room temperature was fixed on carbon double-sided tape for SEM, and then vapor-deposited with gold. The samples were observed at an accelerating voltage of 20 kV.

In a composition in which aggregates are observed, the average Feret diameter is the average value of the Feret diameters of 20 aggregates.

"Observation of Perovskite Compounds Using Transmission Electron Microscopy"

The perovskite compound was observed using a transmission electron microscope (JEM-2200FS, manufactured by Nippon Electronics Co., Ltd.). For the observation sample, the perovskite compound was extracted from the perovskite compound-containing dispersion liquid composition onto the grid with a support film, and then observed at an accelerating voltage of 200 kV.

The average Feret diameter is an average value of the Feret diameters of 20 perovskite compounds.

(synthesis of composition)

[Example 1]

Mix 0.814 g cesium carbonate, 40 mL 1-octadecene solvent, and 2.5 mL oleic acid. Stir with a magnetic stirrer, and heat at 150° C. for 1 hour while blowing nitrogen gas, to prepare a cesium carbonate solution 1 .

0.276 g of lead bromide (PbBr ₂ ) was mixed with 20 mL of 1-octadecene solvent. After stirring with a magnetic stirrer and heating at 120° C. for 1 hour while blowing nitrogen, 2 mL of oleic acid and 2 mL of oleylamine were added to prepare a lead bromide dispersion.

After heating the lead bromide dispersion to a temperature of 160° C., 1.6 mL of the cesium carbonate solution 1 was added thereto. After the addition, the reaction container was immersed in ice water and cooled to room temperature to obtain a dispersion liquid.

Next, the dispersion was centrifuged at 10,000 rpm for 5 minutes to separate the precipitate to obtain perovskite compound 1 as a precipitate. After dispersing the perovskite compound 1 in 5 mL of n-hexane, 100 μL of the dispersion was collected and dispersed in 0.9 mL of n-hexane to obtain a dispersion 1 containing the perovskite compound 1 and a solvent.

The concentration of perovskite compound 1 measured by ICP-MS and ion chromatography was 2000 ppm (μg/g).

After diluting the perovskite compound 1 with n-hexane to 200 ppm (μg/g), the peak wavelength of the emission spectrum measured with a quantum yield measuring device was 523 nm.

The X-ray diffraction pattern of the compound recovered by natural drying of the solvent was measured with an X-ray diffraction measuring device (XRD, CuKα ray, X'pertPROMPD, manufactured by Seiko Co., Ltd.). The (001) peak was confirmed to have a three-dimensional perovskite crystal structure.

The average Feret diameter of the perovskite compound observed with TEM was 11 nm.

Then, 0.110 g of lead bromide (PbBr ₂ ) and 0.208 g of lead iodide (PbI ₂ ) were mixed with 20 mL of 1-octadecene solvent. After stirring with a magnetic stirrer and heating at 120° C. for 1 hour while blowing nitrogen gas, 2 mL of oleic acid and 2 mL of oleylamine were added to prepare a lead bromide-lead iodide dispersion.

After the lead bromide-lead iodide dispersion liquid was heated to a temperature of 160° C., 1.6 mL of the cesium carbonate solution 1 was added thereto. After the addition, the reaction container was immersed in ice water and cooled to room temperature to obtain a dispersion liquid.

Next, the dispersion liquid was centrifuged at 10,000 rpm for 5 minutes to separate the precipitate, and the precipitate perovskite compound 2 was obtained. After dispersing the perovskite compound 2 in 5 mL of n-hexane, 100 μL of the dispersion was collected and dispersed in 0.9 mL of n-hexane to obtain a dispersion 2 containing the perovskite compound 2 and a solvent.

The average Feret diameter of the perovskite compound observed by TEM was 19 nm.

The concentration of perovskite compound 2 measured by ICP-MS and ion chromatography was 2000 ppm (μg/g).

After diluting the perovskite compound 2 with n-hexane to 200 ppm (μg/g), the peak wavelength of the emission spectrum measured with a quantum yield measuring device was 638 nm.

After mixing 3 µL of 4-vinylbenzylamine in the dispersion liquid 1 containing the above-mentioned perovskite compound 1 and the solvent, 30 mg of 2,2'-azobisisobutyronitrile was mixed. After replacing with nitrogen, polymerization was carried out at 60° C. with a stirrer for 4 hours to obtain a composition. In the composition, the mass ratio is perovskite compound 1/4-vinylbenzylamine=0.045.

After diluting the perovskite compound 1 with n-hexane to 200 ppm (μg/g), the peak of the emission spectrum measured with a quantum yield measuring device was 521 nm.

Furthermore, 0.1 mL of the above-mentioned composition and 0.1 mL of the dispersion liquid 2 containing the perovskite compound 2 and the solvent were mixed in 0.8 mL of n-hexane. The emission spectrum after mixing was measured with a quantum yield measuring device. As a result, the peak at 530 nm, which is the peak emission wavelength of the perovskite compound 1, and the peak at 622 nm, which is the peak emission wavelength of the perovskite compound 2, were maintained, respectively.

The absolute value of (luminescence peak wavelength (nm) of perovskite compound 1 before mixing)-(luminescence peak wavelength (nm) of perovskite compound 1 after mixing) is 9nm, (perovskite compound 2 before mixing The absolute value of the emission peak wavelength (nm))-(the emission peak wavelength (nm) of the mixed perovskite compound 2) was 16 nm.

[Example 2]

A composition was obtained in the same manner as in Example 1 above, except that 10 μL of 4-vinylbenzylamine was used and the mass ratio [perovskite compound 1]/[4-vinylbenzylamine]=0.013.

After diluting the perovskite compound 1 with n-hexane to 200 ppm (μg/g), the peak wavelength of the emission spectrum measured with a quantum yield measuring device was 522 nm.

Furthermore, 0.1 mL of the above-mentioned composition and 0.1 mL of the dispersion liquid 2 containing the perovskite compound 2 and the solvent were mixed in 0.8 mL of n-hexane. The emission spectrum after mixing was measured with a quantum yield measuring device. The result is shown in Figure 3.

As shown in FIG. 3 , when dispersion liquid 2 is mixed with the composition of Example 2, the peak emission peak wavelength of perovskite compound 1, which is 520 nm, and the peak emission wavelength of perovskite compound 2, which is 645 nm, are maintained, respectively. Peak.

The absolute value of (luminescence peak wavelength (nm) of perovskite compound 1 before mixing)-(luminescence peak wavelength (nm) of perovskite compound 1 after mixing) is 2 nm, and (perovskite compound before mixing The absolute value of the emission peak wavelength (nm) of 2)-(the emission peak wavelength (nm) of the mixed perovskite compound 2) was 7 nm.

[Example 3]

After mixing 10 mg of 4-carboxystyrene into the dispersion 1 containing the perovskite compound 1 and the solvent described in Example 1, 30 mg of 2,2'-azobisisobutyronitrile was mixed. After replacing with nitrogen, it polymerized while stirring with a stirrer at 60 degreeC for 1 hour, and obtained the composition. In the composition, the mass ratio was [perovskite compound 1]/[4-carboxystyrene]=0.013.

After diluting the perovskite compound 1 with n-hexane to 200 ppm (μg/g), the peak wavelength of the emission spectrum measured with a quantum yield measuring device was 522 nm.

0.1 mL of the above composition and 0.1 mL of the dispersion liquid 2 containing the perovskite compound 2 and the solvent were mixed into 0.8 mL of n-hexane. The emission spectrum after mixing was measured with a quantum yield measuring device. As a result, the peak at 541 nm, which is the peak emission wavelength of the perovskite compound 1, and the peak at 634 nm, which is the peak emission wavelength of the perovskite compound 2, were maintained, respectively.

The absolute value of (luminescence peak wavelength (nm) of perovskite compound 1 before mixing)-(luminescence peak wavelength (nm) of perovskite compound 1 after mixing) is 19 nm, and (perovskite compound before mixing The absolute value of the emission peak wavelength (nm) of 2)-(the emission peak wavelength (nm) of the mixed perovskite compound 2) was 4 nm.

[Example 4]

A composition was obtained in the same manner as in Example 3 above, except that 30 mg of 4-carboxystyrene was used and the mass ratio [perovskite compound 1]/[4-carboxystyrene]=0.0044.

After diluting the perovskite compound 1 with n-hexane to 200 ppm (μg/g), the peak of the emission spectrum measured with a quantum yield measuring device was 522 nm.

0.1 mL of the above composition and 0.1 mL of the dispersion liquid 2 containing the perovskite compound 2 and the solvent were mixed into 0.8 mL of n-hexane. The emission spectrum after mixing was measured with a quantum yield measuring device. The result is shown in Figure 3.

As shown in FIG. 3 , when dispersion liquid 2 is mixed with the composition of Example 4, the peak emission peak wavelength of perovskite compound 1, which is 516 nm, and the peak emission wavelength of perovskite compound 2, which is 642 nm, are maintained, respectively. Peak.

The absolute value of (luminescence peak wavelength (nm) of perovskite compound 1 before mixing)-(luminescence peak wavelength (nm) of perovskite compound 1 after mixing) is 6 nm, and (perovskite compound before mixing The absolute value of the emission peak wavelength (nm) of 2)-(the emission peak wavelength (nm) of the mixed perovskite compound 2) was 4 nm.

[Example 5]

After mixing 10 mg of 2-acrylamide-2-methylpropanesulfonic acid in the dispersion liquid 1 containing the perovskite compound 1 and the solvent described in Example 1, 30 mg of 2,2'-azobisisobutyronitrile was mixed. After replacing with nitrogen, it polymerized while stirring with a stirrer at 60 degreeC for 1 hour, and obtained the composition. In the composition, the mass ratio was [perovskite compound 1]/[2-acrylamide-2-methylpropanesulfonic acid]=0.013.

After diluting the perovskite compound 1 with n-hexane to 200 ppm (μg/g), the peak wavelength of the emission spectrum measured with a quantum yield measuring device was 521 nm.

0.1 mL of the above composition and 0.1 mL of the dispersion liquid 2 containing the perovskite compound 2 and the solvent were mixed into 0.8 mL of n-hexane. The emission spectrum after mixing was measured with a quantum yield measuring device. As a result, the peak at 523 nm, which is the peak emission wavelength of the perovskite compound 1, and the peak at 631 nm, which is the peak emission wavelength of the perovskite compound 2, were maintained, respectively.

The absolute value of (luminescence peak wavelength (nm) of perovskite compound 1 before mixing)-(luminescence peak wavelength (nm) of perovskite compound 1 after mixing) is 2 nm, and (perovskite compound before mixing The absolute value of the emission peak wavelength (nm) of 2)-(the emission peak wavelength (nm) of the mixed perovskite compound 2) was 7 nm.

[Example 6]

After mixing 10 mg of 3-[[2-(methacryloyloxy)ethyl]dimethylammonium]propionate in the dispersion 1 containing the perovskite compound 1 and the solvent described in Example 1, Mix 30 mg of 2,2'-azobisisobutyronitrile. After replacing with nitrogen, it polymerized while stirring with a stirrer at 60 degreeC for 1 hour, and obtained the composition. In the composition, the mass ratio was [perovskite compound 1]/[3-[[2-(methacryloyloxy)ethyl]dimethylammonium]propionate]=0.013.

After diluting the perovskite compound 1 with n-hexane to 200 ppm (μg/g), the peak wavelength of the emission spectrum measured with a quantum yield measuring device was 518 nm.

0.1 mL of the above composition and 0.1 mL of the dispersion liquid 2 containing the perovskite compound 2 and the solvent were mixed into 0.8 mL of n-hexane. The emission spectrum after mixing was measured with a quantum yield measuring device. As a result, the peak at 523 nm, which is the peak emission wavelength of the perovskite compound 1, and the peak at 631 nm, which is the peak emission wavelength of the perovskite compound 2, were maintained, respectively.

The absolute value of (luminescence peak wavelength (nm) of perovskite compound 1 before mixing)-(luminescence peak wavelength (nm) of perovskite compound 1 after mixing) is 5 nm, and (perovskite compound before mixing The absolute value of the emission peak wavelength (nm) of 2)-(the emission peak wavelength (nm) of the mixed perovskite compound 2) was 7 nm.

[Example 7]

In addition to making 20 mg of 3-[[2-(methacryloyloxy)ethyl]dimethylammonium] propionate, the mass ratio of [perovskite compound 1]/[3-[[2-(methacrylic Except for acyloxy)ethyl]dimethylammonium]propionate] = 0.0065, a composition was obtained in the same manner as in Example 6 above.

After diluting the perovskite compound 1 with n-hexane to 200 ppm (μg/g), the peak wavelength of the emission spectrum measured with a quantum yield measuring device was 520 nm.

0.1 mL of the above composition and 0.1 mL of the dispersion liquid 2 containing the perovskite compound 2 and the solvent were mixed into 0.8 mL of n-hexane. The emission spectrum after mixing was measured with a quantum yield measuring device. The results are shown in FIG. 3 .

As shown in FIG. 3 , when the dispersion liquid 2 is mixed with the composition of Example 7, the peak emission peak wavelength of the perovskite compound 1, which is 531 nm, and the peak emission wavelength of the perovskite compound 2, namely, are maintained, respectively. 617nm peak.

The absolute value of (luminescence peak wavelength (nm) of perovskite compound 1 before mixing)-(luminescence peak wavelength (nm) of perovskite compound 1 after mixing) is 11 nm, and (perovskite compound before mixing The absolute value of the emission peak wavelength (nm) of 2 - (the emission peak wavelength (nm) of the mixed perovskite compound 2) was 21 nm.

[Example 8]

After mixing 3 µL of methacrylic acid in the dispersion liquid 1 containing the perovskite compound 1 and the solvent described in Example 1, 30 mg of 2,2'-azobisisobutyronitrile was mixed. After replacing with nitrogen, it polymerized while stirring with a stirrer at 60 degreeC for 1 hour, and obtained the composition. In the composition, the mass ratio was [perovskite compound 1]/[methacrylic acid]=0.043.

After diluting the perovskite compound 1 with n-hexane to 200 ppm (μg/g), the peak wavelength of the emission spectrum measured with a quantum yield measuring device was 519 nm.

0.1 mL of the above composition and 0.1 mL of the dispersion liquid 2 containing the perovskite compound 2 and the solvent were mixed into 0.8 mL of n-hexane. The emission spectrum after mixing was measured with a quantum yield measuring device. As a result, the peak at 531 nm, which is the peak emission wavelength of the perovskite compound 1, and the peak at 633 nm, which is the peak emission wavelength of the perovskite compound 2, were maintained, respectively.

The absolute value of (luminescence peak wavelength (nm) of perovskite compound 1 before mixing)-(luminescence peak wavelength (nm) of perovskite compound 1 after mixing) is 12 nm, and (perovskite compound before mixing The absolute value of the emission peak wavelength (nm) of 2 - (the emission peak wavelength (nm) of the perovskite compound 2 after mixing) was 5 nm.

[Example 9]

A composition was obtained in the same manner as in Example 8 above except that 10 μL of methacrylic acid was used and the mass ratio [perovskite compound 1]/[methacrylic acid]=0.013.

After diluting the perovskite compound 1 with n-hexane to 200 ppm (μg/g), the peak wavelength of the emission spectrum measured with a quantum yield measuring device was 519 nm.

0.1 mL of the above composition and 0.1 mL of the dispersion liquid 2 containing the perovskite compound 2 and the solvent were mixed into 0.8 mL of n-hexane. The emission spectrum after mixing was measured with a quantum yield measuring device. The result is shown in Figure 4.

As shown in FIG. 4 , when dispersion liquid 2 is mixed with the composition of Example 9, the peak emission peak wavelength of perovskite compound 1, which is 522 nm, and the peak emission wavelength of perovskite compound 2, which is 636 nm, are maintained, respectively. Peak.

The absolute value of (luminescence peak wavelength (nm) of perovskite compound 1 before mixing)-(luminescence peak wavelength (nm) of perovskite compound 1 after mixing) is 3 nm, and (perovskite compound before mixing The absolute value of the emission peak wavelength (nm) of 2 - (the emission peak wavelength (nm) of the perovskite compound 2 after mixing) is 2 nm.

[Example 10]

After mixing 5 µL of methacrylic acid in the dispersion liquid 2 containing the perovskite compound 2 and the solvent described in Example 1, 30 mg of 2,2'-azobisisobutyronitrile was mixed. After replacing with nitrogen, it polymerized while stirring with a stirrer at 60 degreeC for 1 hour, and obtained the composition. In the composition, the mass ratio was [perovskite compound 2]/[methacrylic acid]=0.026.

After diluting the perovskite compound 2 with n-hexane to 200 ppm (μg/g), the peak wavelength of the emission spectrum measured with a quantum yield measuring device was 631 nm.

0.1 mL of the above composition and 0.1 mL of dispersion liquid 1 containing perovskite compound 1 and a solvent were mixed into 0.8 mL of n-hexane. The emission spectrum after mixing was measured with a quantum yield measuring device. As a result, the peak at 528 nm, which is the peak emission wavelength of the perovskite compound 1, and the peak at 621 nm, which is the peak emission wavelength of the perovskite compound 2, were maintained, respectively.

The absolute value of (luminescence peak wavelength (nm) of perovskite compound 1 before mixing)-(luminescence peak wavelength (nm) of perovskite compound 1 after mixing) is 5 nm, and (perovskite compound before mixing The absolute value of the emission peak wavelength (nm) of 2)-(the emission peak wavelength (nm) of the mixed perovskite compound 2) was 10 nm.

[Example 11]

A composition was obtained in the same manner as in Example 10 above except that 10 μL of methacrylic acid was used and the mass ratio [perovskite compound 2]/[methacrylic acid]=0.013.

After diluting the perovskite compound 2 with n-hexane to 200 ppm (μg/g), the peak wavelength of the emission spectrum measured with a quantum yield measuring device was 629 nm.

0.1 mL of the above composition and 0.1 mL of dispersion liquid 1 containing perovskite compound 1 and a solvent were mixed into 0.8 mL of n-hexane. The emission spectrum after mixing was measured with a quantum yield measuring device. As a result, the peak at 525 nm, which is the peak emission wavelength of the perovskite compound 1, and the peak at 622 nm, which is the peak emission wavelength of the perovskite compound 2, were maintained, respectively.

The absolute value of (luminescence peak wavelength (nm) of perovskite compound 1 before mixing)-(luminescence peak wavelength (nm) of perovskite compound 1 after mixing) is 2 nm, and (perovskite compound before mixing The absolute value of the emission peak wavelength (nm) of 2)-(the emission peak wavelength (nm) of the mixed perovskite compound 2) was 7 nm.

[Example 12]

A composition was obtained in the same manner as in Example 10 above, except that 30 μL of methacrylic acid was used and the mass ratio [perovskite compound 2]/[methacrylic acid]=0.0043.

After diluting the perovskite compound 2 with n-hexane to 200 ppm (μg/g), the peak wavelength of the emission spectrum measured with a quantum yield measuring device was 630 nm.

0.1 mL of the above composition and 0.1 mL of dispersion liquid 1 containing perovskite compound 1 and a solvent were mixed into 0.8 mL of n-hexane. The emission spectrum after mixing was measured with a quantum yield measuring device. The result is shown in Figure 4.

As shown in FIG. 4 , when dispersion liquid 1 is mixed with the composition of Example 12, the peak emission peak wavelength of perovskite compound 2, which is 626 nm, and the peak emission wavelength of perovskite compound 1, which is 520 nm, are maintained, respectively. Peak.

The absolute value of (luminescence peak wavelength (nm) of perovskite compound 1 before mixing)-(luminescence peak wavelength (nm) of perovskite compound 1 after mixing) is 3 nm, and (perovskite compound before mixing The absolute value of the emission peak wavelength (nm) of 2)-(the emission peak wavelength (nm) of the mixed perovskite compound 2) was 4 nm.

[Example 13]

After mixing 10 µL of 4-vinylbenzylamine in the dispersion liquid 1 containing the perovskite compound 1 and the solvent described in Example 1, 30 mg of 2,2'-azobisisobutyronitrile was mixed. After replacing with nitrogen, it polymerized while stirring with a stirrer at 60 degreeC for 1 hour, and obtained the composition. In the composition, the mass ratio was [Perovskite Compound 1]/[4-vinylbenzylamine]=0.013.

After diluting the perovskite compound 1 with n-hexane to 200 ppm (μg/g), the peak wavelength of the emission spectrum measured with a quantum yield measuring device was 522 nm.

Next, methacrylic resin and toluene were mixed so that methacrylic resin (PMMA, manufactured by Sumitomo Chemical Co., Ltd., Sumitomo methacrylic resin, MH, molecular weight about 120,000, specific gravity 1.2g/ml) was 16.5% by mass, and then It heated at 60 degreeC for 3 hours, and obtained the solution which melt|dissolved a polymer.

0.15 g of the polymer composition containing the above-mentioned perovskite compound 1 and an addition polymerizable compound having an ionic group, and a solvent, 0.15 g of the dispersion liquid 2 containing the perovskite compound 2 and the solvent, and 0.913 g were dissolved. After the polymer solutions were mixed, the solvent was evaporated by natural drying to obtain compositions each having a perovskite compound concentration of 2000 ppm (µg/g).

After the obtained composition was cut into 1 cm×1 cm×100 μm, the emission spectrum was measured with a quantum yield measuring device. The result is shown in Figure 4.

As shown in FIG. 4 , the composition of Example 13 maintained a peak of 532 nm as the emission peak wavelength of perovskite compound 1 and a peak of 624 nm as the emission peak wavelength of perovskite compound 2, respectively.

The absolute value of (luminescence peak wavelength (nm) of perovskite compound 1 before mixing)-(luminescence peak wavelength (nm) of perovskite compound 1 after mixing) is 10 nm, and (perovskite compound before mixing The absolute value of the emission peak wavelength (nm) of 2 - (the emission peak wavelength (nm) of the perovskite compound 2 after mixing) was 14 nm.

[Example 14]

Polysilazane (Durazane 1500 Slow Cure, manufactured by Merck Basmann Materials Co., Ltd.) was mixed with the dispersion liquid 1 containing the perovskite compound 1 and the solvent described in Example 1. In the dispersion liquid, the molar ratio was Si/Pb=76.0. After further mixing 30 µL of methacrylic acid, 30 mg of 2,2'-azobisisobutyronitrile was mixed. After replacing with nitrogen, it polymerized while stirring with a stirrer at 60 degreeC for 1 hour, and obtained the composition. In the composition, the mass ratio was [perovskite compound 1]/[methacrylic acid]=0.0043.

After diluting the perovskite compound 1 with n-hexane to 200 ppm (μg/g), the peak of the emission spectrum measured with a quantum yield measuring device was 518 nm.

0.1 mL of the above composition and 0.1 mL of the dispersion liquid 2 containing the perovskite compound 2 and the solvent were mixed into 0.8 mL of n-hexane. The emission spectrum after mixing was measured with a quantum yield measuring device. The result is shown in Figure 5.

As shown in FIG. 5 , when dispersion liquid 2 is mixed with the composition of Example 14, the peak emission peak wavelength of perovskite compound 1, which is 517 nm, and the peak emission wavelength of perovskite compound 2, which is 639 nm, are maintained, respectively. Peak.

The absolute value of (luminescence peak wavelength (nm) of perovskite compound 1 before mixing)-(luminescence peak wavelength (nm) of perovskite compound 1 after mixing) is 1 nm, and (perovskite compound before mixing The absolute value of the emission peak wavelength (nm) of 2)-(the emission peak wavelength (nm) of the mixed perovskite compound 2) was 1 nm.

The aggregates contained in the composition had an average Feret diameter of 1 μm.

[Example 15]

Polysilazane (Durazane 1500 Slow Cure, manufactured by Merck Basmann Materials Co., Ltd.) was mixed with the dispersion liquid 1 containing the perovskite compound 1 and the solvent described in Example 1. In the dispersion liquid, the molar ratio was Si/Pb=76.0. After further mixing 20 µL of 4-vinylbenzylamine, 30 mg of 2,2'-azobisisobutyronitrile was mixed. After replacing with nitrogen, it polymerized while stirring with a stirrer at 60 degreeC for 1 hour, and obtained the composition. In the composition, the mass ratio was [Perovskite Compound 1]/[4-vinylbenzylamine]=0.0067.

After diluting the perovskite compound 1 with n-hexane to 200 ppm (μg/g), the peak of the emission spectrum measured with a quantum yield measuring device was 520 nm.

0.1 mL of the above composition and 0.1 mL of the dispersion liquid 2 containing the perovskite compound 2 and the solvent were mixed into 0.8 mL of n-hexane. The emission spectrum after mixing was measured with a quantum yield measuring device. As a result, the peak at 527 nm, which is the peak emission wavelength of the perovskite compound 1, and the peak at 619 nm, which is the peak emission wavelength of the perovskite compound 2, were maintained, respectively.

The absolute value of (luminescence peak wavelength (nm) of perovskite compound 1 before mixing)-(luminescence peak wavelength (nm) of perovskite compound 1 after mixing) is 7 nm, and (perovskite compound before mixing The absolute value of the emission peak wavelength (nm) of 2 - (the emission peak wavelength (nm) of the perovskite compound 2 after mixing) was 19 nm.

[Example 16]

Polysilazane (Durazane 1500 SlowCure, manufactured by Merck-Basmann Materials Co., Ltd.) was mixed with the dispersion liquid 2 containing the perovskite compound 2 and the solvent described in Example 1. In the dispersion liquid, the molar ratio was Si/Pb=22.8. After further mixing 5 µL of methacrylic acid, 30 mg of 2,2'-azobisisobutyronitrile was mixed. After replacing with nitrogen, it polymerized while stirring with a stirrer at 60 degreeC for 1 hour, and obtained the composition. In the composition, the mass ratio was [perovskite compound 2]/[methacrylic acid]=0.026.

After diluting the perovskite compound 2 with n-hexane to 200 ppm (μg/g), the peak of the emission spectrum measured with a quantum yield measuring device was 640 nm.

0.1 mL of the above composition and 0.1 mL of dispersion liquid 1 containing perovskite compound 1 and a solvent were mixed into 0.8 mL of n-hexane. The emission spectrum after mixing was measured with a quantum yield measuring device. As a result, the peak emission peak wavelength of the perovskite compound 1 at 518 nm and the peak emission peak wavelength of the perovskite compound 2 at 642 nm were maintained, respectively.

The absolute value of (luminescence peak wavelength (nm) of perovskite compound 1 before mixing)-(luminescence peak wavelength (nm) of perovskite compound 1 after mixing) is 5 nm, and (perovskite compound before mixing The absolute value of the emission peak wavelength (nm) of 2 - (the emission peak wavelength (nm) of the perovskite compound 2 after mixing) is 2 nm.

[Example 17]

Polysilazane (Durazane 1500 SlowCure, manufactured by Merck-Basmann Materials Co., Ltd.) was mixed with the dispersion liquid 2 containing the perovskite compound 2 and the solvent described in Example 1. In the dispersion liquid, the molar ratio was Si/Pb=22.8. After further mixing 10 µL of methacrylic acid, 30 mg of 2,2'-azobisisobutyronitrile was mixed. After replacing with nitrogen, it polymerized while stirring with a stirrer at 60 degreeC for 1 hour, and obtained the composition. In the composition, the mass ratio was [perovskite compound 2]/[methacrylic acid]=0.013.

After diluting the perovskite compound 2 with n-hexane to 200 ppm (μg/g), the peak wavelength of the emission spectrum measured with a quantum yield measuring device was 639 nm.

0.1 mL of the above composition and 0.1 mL of dispersion liquid 1 containing perovskite compound 1 and a solvent were mixed into 0.8 mL of n-hexane. The emission spectrum after mixing was measured with a quantum yield measuring device. As a result, the peak emission peak wavelength of the perovskite compound 1 at 518 nm and the peak emission peak wavelength of the perovskite compound 2 at 640 nm were maintained, respectively.

The absolute value of (luminescence peak wavelength (nm) of perovskite compound 1 before mixing)-(luminescence peak wavelength (nm) of perovskite compound 1 after mixing) is 5 nm, and (perovskite compound before mixing The absolute value of the emission peak wavelength (nm) of 2)-(the emission peak wavelength (nm) of the mixed perovskite compound 2) was 1 nm.

[Example 18]

Polysilazane (Durazane 1500 SlowCure, manufactured by Merck-Basmann Materials Co., Ltd.) was mixed with the dispersion liquid 2 containing the perovskite compound 2 and the solvent described in Example 1. In the dispersion liquid, the molar ratio was Si/Pb=22.8. After further mixing 30 µL of methacrylic acid, 30 mg of 2,2'-azobisisobutyronitrile was mixed. After replacing with nitrogen, it polymerized while stirring with a stirrer at 60 degreeC for 1 hour, and obtained the composition. In the composition, the mass ratio was [perovskite compound 2]/[methacrylic acid]=0.0043.

After diluting the perovskite compound 2 with n-hexane to 200 ppm (μg/g), the peak wavelength of the emission spectrum measured with a quantum yield measuring device was 645 nm.

0.1 mL of the above-mentioned composition and 10.1 mL of a dispersion liquid containing perovskite compound 1 and a solvent were mixed in 0.8 mL of n-hexane. The emission spectrum after mixing was measured with a quantum yield measuring device. The result is shown in Figure 5.

As shown in FIG. 5 , when dispersion liquid 1 is mixed with the composition of Example 18, the peak emission peak wavelength of perovskite compound 1, which is 521 nm, and the peak emission wavelength of perovskite compound 2, which is 647 nm, are maintained, respectively. Peak.

The absolute value of (luminescence peak wavelength (nm) of perovskite compound 1 before mixing)-(luminescence peak wavelength (nm) of perovskite compound 1 after mixing) is 2 nm, and (perovskite compound before mixing The absolute value of the emission peak wavelength (nm) of 2 - (the emission peak wavelength (nm) of the perovskite compound 2 after mixing) is 2 nm.

The average Feret diameter of the aggregates contained in the composition was 0.3 μm.

[Comparative example 1]

0.1 mL of the dispersion liquid 1 containing the perovskite compound 1 and the solvent and 0.1 mL of the dispersion liquid 2 containing the perovskite compound 2 and the solvent described in Example 1 were mixed into 0.8 mL of n-hexane. The emission spectrum after mixing was measured with a quantum yield measuring device. The result is shown in Figure 6.

As shown in FIG. 6 , in Comparative Example 1, a new emission peak wavelength at 559 nm, which is different from the emission peak wavelengths of perovskite compound 1 and perovskite compound 2, was emitted.

The absolute value of (luminescence peak wavelength (nm) of perovskite compound 1 before mixing)-(luminescence peak wavelength (nm) of perovskite compound after mixing) is 36 nm, and (perovskite compound 2 before mixing The absolute value of the emission peak wavelength (nm))-(the emission peak wavelength (nm) of the mixed perovskite compound) was 79 nm.

[Comparative example 2]

After mixing 10 µL of styrene in the dispersion liquid 1 containing the perovskite compound 1 and the solvent described in Example 1, 30 mg of 2,2'-azobisisobutyronitrile was mixed. After replacing with nitrogen, it polymerized while stirring with a stirrer at 60 degreeC for 1 hour, and obtained the composition. In the composition, the mass ratio was [perovskite compound 1]/[styrene]=0.014.

After diluting the perovskite compound 1 with n-hexane to 200 ppm (μg/g), the peak wavelength of the emission spectrum measured with a quantum yield measuring device was 521 nm.

0.1 mL of the above composition and 20.1 mL of a dispersion containing the perovskite compound 2 and a solvent were mixed in 0.8 mL of n-hexane. The emission spectrum after mixing was measured with a quantum yield measuring device. The result is shown in Figure 6.

As shown in FIG. 6 , in Comparative Example 2, a new luminescence peak wavelength at 571 nm different from the luminescence peak wavelengths of perovskite compound 1 and perovskite compound 2 was emitted.

The absolute value of (luminescence peak wavelength (nm) of perovskite compound 1 before mixing)-(luminescence peak wavelength (nm) of perovskite compound 1 after mixing) is 50 nm, and (perovskite compound before mixing The absolute value of the emission peak wavelength (nm) of 2 - (the emission peak wavelength (nm) of the perovskite compound 2 after mixing) was 67 nm.

[Comparative example 3]

After mixing 10 µL of methyl methacrylate in the dispersion 1 containing the perovskite compound 1 and the solvent described in Example 1, 30 mg of 2,2'-azobisisobutyronitrile was mixed. After replacing with nitrogen, it polymerized while stirring with a stirrer at 60 degreeC for 1 hour, and obtained the composition. In the composition, the mass ratio [perovskite compound 1]/[methyl methacrylate]=0.014.

After diluting the perovskite compound 1 with n-hexane to 200 ppm (μg/g), the peak wavelength of the emission spectrum measured with a quantum yield measuring device was 521 nm.

0.1 mL of the above composition and 20.1 mL of a dispersion containing the perovskite compound 2 and a solvent were mixed in 0.8 mL of n-hexane. The emission spectrum after mixing was measured with a quantum yield measuring device. The result is shown in Figure 6.

As shown in FIG. 6 , in Comparative Example 3, a new luminescence peak wavelength of 545 nm different from the luminescence peak wavelengths of perovskite compound 1 and perovskite compound 2 was emitted.

The absolute value of (luminescence peak wavelength (nm) of perovskite compound 1 before mixing)-(luminescence peak wavelength (nm) of perovskite compound 1 after mixing) is 24 nm, and (perovskite compound before mixing The absolute value of the emission peak wavelength (nm) of 2)-(the emission peak wavelength (nm) of the mixed perovskite compound 2) was 93 nm.

In Table 1 below, the compositions of Examples 1 to 18 and Comparative Examples 1 to 3, and the results of evaluations 1 and 2 of the emission peaks when two types of perovskite compounds were mixed are described. In Table 1, "(1) component/(2) component (mass ratio)" indicates that the mass of the perovskite compound ((1) component) contained in the composition is divided by the addition polymerization having an ionic group The mass ratio obtained by the mass of the active compound or its polymer ((2) component).

Table 1

From the above results, it can be seen that the compositions of Examples 1 to 18 of the present invention in which two kinds of perovskite compounds are mixed can maintain the intensity of each perovskite compound even if two kinds of perovskite compounds having different emission wavelengths are mixed. Intrinsic emission wavelength. In contrast, in Comparative Examples 1 to 3, an emission peak at a new wavelength different from the intrinsic emission wavelength of each perovskite compound was emitted.

[Reference example 1]

After removing the solvent from the compositions described in Examples 1 to 18 if necessary, put them into a glass tube or the like and seal them, and then arrange them between a blue light-emitting diode as a light source and a light guide plate, thereby manufacturing a blue A backlight that converts blue light from LEDs into green or red light.

[Reference example 2]

Resin compositions can be obtained by removing the solvent from the compositions described in Examples 1 to 18 as needed, and then forming a sheet to obtain a resin composition, which is sandwiched between two barrier films and sealed on a light guide plate to manufacture A backlight that can convert blue light irradiated from a blue light-emitting diode placed on the end surface (side surface) of the light guide plate to the above-mentioned sheet through the light guide plate into green light or red light.

[Reference example 3]

A backlight capable of converting irradiated blue light into green light or red light was produced by disposing the composition described in Examples 1 to 18 near the light emitting part of the blue light emitting diode after removing the solvent as necessary.

[Reference example 4]

A wavelength converting material can be obtained by removing the solvent from the composition described in Examples 1 to 18 as necessary, mixing the resist and removing the solvent. By arranging the obtained wavelength conversion material between a blue light emitting diode as a light source and a light guide plate or in the rear stage of an OLED as a light source, a backlight capable of converting blue light from a light source into green or red light is produced.

[Reference example 5]

LEDs were obtained by mixing the compositions described in Examples 1 to 18 with conductive particles such as ZnS to form a film, laminating an n-type transport layer on one side and laminating a p-type transport layer on the other side. By passing an electric current, the holes of the p-type semiconductor and the electrons of the n-type semiconductor cancel the charges in the perovskite compound at the junction surface, thereby making it possible to emit light.

[Reference example 6]

A dense titanium oxide layer was laminated on the surface of a fluorine-doped tin oxide (FTO) substrate, a porous aluminum oxide layer was laminated thereon, and the composition described in Examples 1 to 18 was laminated thereon, and after the solvent was removed, the A hole transport layer such as 2,2',7,7'-tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9'-spirobifluorene (Spiro-OMeTAD) is stacked on top, A silver (Ag) layer is laminated on it to make a solar cell.

[Reference example 7]

After mixing the compositions described in Examples 1 to 18 with the resin, removing the solvent and performing molding, a resin composition containing the composition of the present invention can be obtained, and by placing it in the rear stage of the blue light-emitting diode, it is possible to manufacture Laser diode illumination that converts blue light irradiated from a blue light-emitting diode to the resin molded body into green light or red light to emit white light.

[industrial availability]

According to the present invention, a composition containing two kinds of perovskite compounds and showing two luminescence peaks can be provided. Furthermore, a film, a laminated structure, and a display can be provided using the said composition.

Explanation of reference signs

1a...first laminated structure, 1b...second laminated structure, 10...film, 20...first substrate, 21...second substrate, 22...sealing layer, 2...light emitting device, 3...display, 30 light source, 40 …LCD panel, 50…prism sheet, 60…light guide plate

Claims (14)

1. A luminous composition comprising the following (1) component, the following (1)-1 component and the following (2) component, and the (1) component and the (2) component The mass ratio (1)/(2) is more than 0.001 and less than 1; (1) Composition: Perovskite compound composed of A, B and X A is a component located at each apex of a hexahedron centered on B in the perovskite crystal structure, and is a monovalent cation, X represents a component located at each apex of an octahedron centered on B in the perovskite crystal structure, and is at least one anion selected from halide ions and thiocyanate ions, B is a component located in the center of a hexahedron with A at its apex and an octahedron with X at its apex in the perovskite crystal structure, and is a metal ion; (1)-1 component: a perovskite compound having a light emission peak wavelength different from that of the above-mentioned component (1) The difference between the luminescence peak wavelength of the component (1)-1 and the luminescence peak wavelength of the component (1) is not less than 70nm and not more than 140nm; (2) Component: an addition polymerizable compound having an ionic group or a polymer obtained by self-polymerizing one type of addition polymerizable compound having an ionic group. 2. The composition according to claim 1, wherein the component (2) is a radically polymerizable compound, an ionically polymerizable compound, or a polymer thereof. 3. The composition according to claim 1, wherein the addition polymerizable compound having an ionic group is selected from acrylic esters having an ionic group and derivatives thereof, ionic group-containing At least one of methacrylates and derivatives thereof, and styrenes having an ionic group and derivatives thereof. 4. The composition according to any one of claims 1 to 3, wherein the component (2) is a polymer of an addition polymerizable compound having an ionic group, and the component (1) and the component The above-mentioned (2) component forms an aggregate. 5. The composition according to any one of claims 1 to 3, further comprising at least one selected from the following (3) component and the following (4) component, (3) Composition: solvent (4) Component: polymerizable compound or polymer thereof. 6. The composition according to any one of claims 1 to 3, further comprising the following (4') component; the total content ratio of (1) component, (2) component and (4') component is relatively The total mass of the composition is more than 90% by mass; (4') Composition: polymer. 7. The composition according to any one of claims 1 to 3, further comprising the following component (5), (5) Component: at least one selected from ammonia, amines, carboxylic acids, and their salts or ions. 8. The composition according to any one of claims 1 to 3, further comprising the following component (6), (6) Component: one or more compounds selected from the group consisting of an organic compound having an amino group, an alkoxy group, and a silicon atom, and a silazane or a modified product thereof. 9. The composition according to claim 8, wherein the component (6) is polysilazane or a modified product thereof. The film using the composition in any one of Claims 1-9. 11. A laminated structure comprising the film according to claim 10. 12. A light-emitting device comprising the laminated structure according to claim 11. 13. A display comprising the laminated structure according to claim 11. 14. A method for producing a composition, characterized in that: A step of dispersing the following (1) component into the following (3) component to obtain a dispersion; The obtained dispersion is mixed with the following (2') components to obtain a mixed solution; A step of performing a polymerization treatment on the obtained mixed liquid to obtain a mixed liquid containing a polymer of an addition polymerizable compound having an ionic group; A step of mixing the obtained polymer mixture containing one type of addition polymerizable compound having an ionic group with the following (4) component; A step of mixing the following (1)-1 component in the obtained mixed solution containing the (4) component; The mass ratio (1)/(2') of the (1) component to the (2') component is 0.001 to 1; (1) Composition: Perovskite compound composed of A, B and X A is a component located at each apex of a hexahedron centered on B in the perovskite crystal structure, and is a monovalent cation, X represents a component located at each apex of an octahedron centered on B in the perovskite crystal structure, and is at least one anion selected from halide ions and thiocyanate ions, B is a component located in the center of a hexahedron with A at its apex and an octahedron with X at its apex in the perovskite crystal structure, and is a metal ion. (1)-1 component: a perovskite compound having a light emission peak wavelength different from that of the above-mentioned component (1) The difference between the emission peak wavelength of the component (1)-1 and the emission peak wavelength of the component (1) is not less than 70 nm and not more than 140 nm, (2') Component: Addition polymerizable compound having an ionic group (3) Composition: solvent (4) Component: polymerizable compound or polymer thereof.

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