CN110799626B

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

Info

Publication number: CN110799626B
Application number: CN201880041030.3A
Authority: CN
Inventors: 内藤翔太
Original assignee: Sumitomo Chemical Co Ltd
Current assignee: Sumitomo Chemical Co Ltd
Priority date: 2017-06-23
Filing date: 2018-06-22
Publication date: 2023-02-28
Anticipated expiration: 2038-06-22
Also published as: CN110799626A; TW201906985A; WO2018235948A1; JPWO2018235948A1; TWI758502B; JP7096818B2

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

Composition, film, laminated structure, light-emitting device, display, and method for producing composition

Technical Field

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

The present application claims priority in Japanese application No. 2017-123597, based on 2017, 6, 23, the contents of which are incorporated herein by reference.

Background

LED backlights have been developed that have a blue LED and a composition comprising two compounds having different emission wavelengths. In recent years, perovskite compounds have been increasingly attracting attention as luminescent compounds contained in the above compositions.

For example, as a composition containing a perovskite compound, a composition in which 2 layers each containing a different perovskite compound are stacked has been reported (non-patent document 1).

Documents of the prior art

Non-patent document

Non-patent document 1: xiaoming Li, ye Wu, shengli Zhang, bo Cai, yu Gu, jizhong Song, haibo Zeng, adv. Funct. Mater.,26, 2435-2445 (2016)

Disclosure of Invention

Technical problem to be solved by the invention

However, the laminated composition described in non-patent document 1 requires a step for forming a plurality of layers, and thus the productivity is not sufficient.

Therefore, the present inventors have conceived that if 1 layer is formed using a composition in which a plurality of perovskite compounds are mixed to obtain light having different emission wavelengths, the number of steps can be reduced, productivity can be improved, and a composition in which 2 perovskite compounds having different emission wavelengths are mixed can be manufactured.

In this study, the following new problems were faced: as a result of measuring the emission wavelength of the obtained composition, the emission wavelength specific to each perovskite compound disappears, and light having a new emission wavelength different from the emission wavelength specific to each perovskite compound is emitted.

The present invention has been made in view of the above problems, and an object thereof is to provide a composition capable of maintaining the emission wavelength specific to each perovskite compound even when a plurality of perovskite compounds having different emission wavelengths are mixed, a method for producing the same, and a film, a laminate structure, a light-emitting device, and a display using the same.

In order to solve the above problems, an object of the present invention is to provide a vehicle steering apparatus including:

as a result of intensive studies to solve the above problems, the present inventors have found that a composition obtained by mixing a plurality of perovskite compounds with a composition containing a perovskite compound and an addition polymerizable compound having an ionic group or a polymer thereof can maintain the luminescence wavelength specific to each perovskite compound.

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

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

(1) The components: perovskite compound containing A, B and X as constituent components

(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 represents a component located at each vertex of an octahedron centering on B in the perovskite crystal structure, and is at least 1 anion selected from a halide ion and a thiocyanate ion.

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

(2) The components: addition polymerizable compound having ionic group or polymer thereof

[2] The composition according to item [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 at least one selected from the group consisting of acrylates having an ionic group and derivatives thereof, methacrylates having an ionic group and derivatives thereof, and styrenes having an ionic group 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) and the component (2) form an aggregate.

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

(3) The components: solvent(s)

(4) The components: polymerizable compound or polymer thereof

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

(4') component (A): polymer and method of making same

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

(5) The components: at least 1 selected from ammonia, amines and carboxylic acids, and their salts or ions

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

(6) The components: at least 1 compound selected from the group consisting of organic compounds having amino group, alkoxy group and silicon atom, and silazane or its modified body

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

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

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

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

[12] A laminated structure comprising the film of [11 ].

[13] A light-emitting device comprising the laminated structure according to [12 ].

[14] A display device comprising the laminated structure according to [12 ].

[15] A method of making a composition, comprising: a step of dispersing the following component (1) in the following component (3) to obtain a dispersion liquid; mixing the obtained dispersion liquid with the following component (2') to obtain a mixed liquid; a step of obtaining a mixed solution of a polymer containing an addition polymerizable compound having an ionic group by performing a polymerization treatment on the obtained mixed solution; and (3) mixing the obtained mixed solution containing the polymer of the addition polymerizable compound having an ionic group with the following component (4).

(1) The components: perovskite compound having A, B and X as constituent components

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

(2') component (a): addition polymerizable compound having ionic group

(3) The components: solvent(s)

(4) The components: polymerizable compound or polymer thereof

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

[17] The method for producing a composition according to [15], further comprising a step of mixing the components (1) -1 after the step of mixing the component (4) with a mixture solution containing the polymer of the addition polymerizable compound having an ionic group.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, it is possible to provide a composition which can maintain the inherent emission wavelength of each perovskite compound even when a plurality of perovskite compounds having different emission wavelengths are mixed, a method for producing the same, and a film, a laminate structure, a light-emitting device, and a display using the same.

Drawings

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

Fig. 2 is a sectional view showing one embodiment of a display of the present invention.

FIG. 3 is a graph showing the measurement results of the luminescence spectra of the compositions of examples 2,4 and 7.

FIG. 4 is a graph showing the measurement results of the luminescence spectra of the compositions of examples 9, 12 and 13.

FIG. 5 is a graph showing the measurement results of the luminescence spectra of the compositions of examples 14 and 18.

FIG. 6 is a graph showing the measurement results of the luminescence spectra of the compositions of comparative examples 1,2 and 3.

Detailed Description

< composition >

The composition of the present embodiment has luminescence. By "luminescence of the composition" is meant the property of the composition to emit light. The composition preferably has a property of emitting light by absorption of excitation energy, and more preferably has a property of emitting light by excitation of excitation light. The wavelength of the excitation light may be, for example, 200nm to 800nm, 250nm to 750nm, or 300nm to 700 nm.

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

(1) A perovskite compound having a, B and X as constituent components. Hereinafter, the term "component (1)" is used.

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.

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

(2) The components: an addition polymerizable compound having an ionic group or a polymer thereof. Hereinafter, the term "component (2)" is used.

It is presumed that the composition of the present embodiment contains the component (2) to form a protective region in the vicinity of the perovskite compound. Thus, when perovskite compounds having emission peak wavelengths different from those of the component (1) are mixed, it is possible to suppress the disappearance of the emission wavelengths unique to the respective perovskite compounds and the generation of light having new emission wavelengths different from the emission wavelengths unique to the respective perovskite compounds. Therefore, it is considered that the inherent luminescence wavelength of each perovskite compound can be maintained.

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

The form of the aggregate containing the components (1) and (2) is not limited as long as the effects of the present invention can be obtained. In the present embodiment, for example, an aggregate containing the component (1) and the component (2) may be formed by association of the component (1) covered with the component (2). In the present embodiment, for example, the (1) component is associated with each other to form an aggregate, and the (2) component covers the surface of the aggregate, whereby an aggregate containing the (1) component and the (2) component can be formed.

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

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

In the composition of the present embodiment, as a method for observing an aggregate containing the component (1) and the component (2), for example, a method for observing the composition using a Scanning Electron Microscope (SEM), a Transmission Electron Microscope (TEM), or the like can be cited. Further, by energy dispersive X-ray analysis (EDX measurement) using SEM or TEM, a detailed element distribution can be analyzed.

For example, by EDX measurement using SEM or TEM, the formation of an aggregate containing the component (1) and the component (2) can be confirmed by blocking the interface between particles containing the element derived from the component (1) by the region containing the element derived from the component (2).

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

In the present specification, the "feret diameter" refers to the maximum distance between two parallel straight lines that sandwich an observation target (aggregate) on a TEM or SEM image. The average Ferrett diameter of the aggregates can be calculated by, for example, observing 20 or more aggregates by SEM or TEM and averaging the observed aggregates. More specifically, for example, 20 aggregates are observed by SEM or TEM, and the average value is taken to obtain the average feret diameter of the aggregates.

When the average feret diameter of the aggregate is not less than the lower limit, a protective region is formed in the vicinity of the component (1), and when a plurality of perovskite compounds having emission peak wavelengths different from those of the component (1) are mixed, it is possible to further suppress the disappearance of the emission wavelengths unique to the respective perovskite compounds and the generation of new emission wavelengths different from the emission wavelengths unique to the respective perovskite compounds. This can further maintain the luminescence wavelength specific to each perovskite compound. Further, when the average Ferrett diameter of the aggregate is not more than the above upper limit, the dispersibility in the solvent or the resin is improved. In the present embodiment, "a plurality of perovskite compounds" means 2 or more perovskite compounds, and preferably 2 perovskite compounds. When 2 kinds of perovskite compounds are contained, it is preferable to contain the component (1) and the perovskite compound (1) -1 component having an emission peak wavelength different from that of the component (1).

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

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

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

Even when an aggregate of the component (1) and the component (2) is associated with an aggregate of the component (1) -1 and the component (2) to form an aggregate of the component (1) and the component (2) and the component (1) -1, a protective region by the component (2) is present at an interface between the component (1) and the component (1) -1, and contact between the component (1) and the component (1) -1 is suppressed, it is considered that the effect of the present invention can be obtained.

From the viewpoint of maintaining the visible light transmittance, the average Ferrett diameter of the aggregate of the (1) -1 component and the (2) component is preferably 20 μm or less. The method of calculating the average Feret diameter of the aggregate of the components (1) -1 and (2) includes a method of calculating the average Feret diameter of the aggregate of the components (1) and (2).

The composition of the present embodiment preferably further contains at least 1 selected from the group consisting of the following component (3) and the following component (4).

(3) The components: and (3) a solvent. Hereinafter, the term "component (3)" is used.

(4) The components: a polymerizable compound or a polymer thereof. However, the components (2) are not limited to the above components. Hereinafter, the term "component (4)" is used.

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

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

(5) The components: at least one compound or ion selected from ammonia, amines, carboxylic acids, and salts or ions thereof. Hereinafter, the term "component (5)" is used.

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

(6) The components: 1 or more compounds selected from the group consisting of organic compounds having an amino group, an alkoxy group, and a silicon atom, and silazanes or modified silazanes thereof.

In the present specification, the term "modified silazane" refers to a compound produced by modifying a silazane. The modification treatment method will be described later.

The composition of the present embodiment may contain other components than the components (1) to (6).

Examples of the other components include impurities, a compound having an amorphous structure composed of an element component constituting the perovskite compound, and a polymerization initiator.

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

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

(4') component (A): a polymer.

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

In the composition of the present embodiment, the total content ratio of the component (1), the component (2), and the component (4') may be 95% by mass or more, may be 99% by mass or more, and may be 100% by mass, based on the total mass of the composition.

The composition of the present embodiment may further contain either one or both of the component (5) and the component (6). The components other than the components (1), (2), (4'), (5) and (6) may be the same as the other components.

In the composition of the embodiment containing the component (1) and the component (2) as essential components and further containing at least 1 selected from the component (3) and the component (4), the content ratio of the component (1) to the total mass of the composition is not particularly limited as long as the effect of the present invention is obtained. In the composition of the present embodiment, the upper limit and the lower limit of the content ratio of the component (1) are preferably in the following ranges with respect to the total mass of the composition from the viewpoint of making it difficult to agglomerate the perovskite compound and from the viewpoint of preventing concentration quenching.

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

The above upper limit value and lower limit value may be arbitrarily combined.

(1) The content ratio of the components relative to the total mass of the composition is generally: 0.0001-50 mass%.

(1) The content ratio of the component (b) is preferably 0.0001 to 1% by mass, more preferably 0.0005 to 1% by mass, and still more preferably 0.001 to 0.5% by mass, based on the total mass of the composition.

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 range is preferable in terms of the difficulty in causing aggregation of the component (1) and the exertion of high luminescence.

In the composition of the embodiment in which the component (1) and the component (2) are essentially constituted and at least 1 selected from the component (3) and the component (4) is further contained, the content ratio of the component (2) to the total mass of the composition 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 the component (1) in the components (3) and (4), the upper limit and the lower limit of the content ratio of the component (2) to the total mass of the composition are preferably in the following ranges.

Specifically, the upper limit value is preferably 50% by mass or less, more preferably 30% by mass or less, and still more preferably 10% by mass or less. In addition, from the viewpoint of maintaining the inherent luminescence wavelength of each perovskite compound in a composition in which a plurality of perovskite compounds are mixed, the lower limit value is preferably 0.001 mass% or more, more preferably 0.01 mass% or more, and even more preferably 0.1 mass% or more.

The above upper limit value and lower limit value may be arbitrarily combined.

(2) The content of the component (b) is usually 0.001 to 50% by mass based on the total mass of the composition.

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

In the composition of the present embodiment, a composition in which the content ratio of the component (2) to the total mass of the composition is within the above range is preferable from the viewpoint of stably dispersing the component (1) in the components (3) and (4), in a composition in which a plurality of perovskite compounds are mixed, from the viewpoint of maintaining the inherent luminescence wavelength of each perovskite compound.

In the composition of the embodiment containing the component (1) and the component (2) as essential components and further containing at least 1 selected from the component (3) and the component (4), the total content ratio of the component (1) and the component (2) to the total mass of the composition is not particularly limited as long as the effect of the present invention is obtained.

In the present embodiment, the total content ratio of the component (1) and the component (2) relative to the total mass of the composition is preferably in the following range from the viewpoint of making it difficult to agglomerate the perovskite compound and the viewpoint of preventing concentration quenching.

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

The above upper limit value and lower limit value may be arbitrarily combined.

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

(1) The total content of the component (i) and the component (2) is preferably 0.001 to 40 mass%, more preferably 0.002 to 30 mass%, and still more preferably 0.005 to 20 mass%, based on the total mass of the composition.

In the composition of the present embodiment, a composition in which the total content ratio of the component (1) and the component (2) is within the above range with respect to the total mass of the composition is preferable from the viewpoint that aggregation of the component (1) is less likely to occur and the light-emitting property is also favorably exhibited.

In the composition of the embodiment containing the essential components of the component (1), the component (2) and the component (4 '), the total content of the component (1), the component (2) and the component (4') is 90% by mass or more based on the total mass of the composition, and the content of the component (1) based on the total mass of the composition is not particularly limited as long as the effect of the present invention is obtained. In the present embodiment, 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 or less, and still more preferably 0.5% by mass or less, from the viewpoint of making the component (1) less likely to aggregate and the viewpoint of preventing concentration quenching.

From the viewpoint of obtaining a good light emission intensity, the content ratio of the component (1) 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 value and lower limit value may be arbitrarily combined.

(1) The content of the component (b) is usually 0.0001 to 50% by mass based on the total mass of the composition.

(1) The content ratio of the component (b) is preferably 0.0001 to 1% by mass based on the total mass of the composition. More preferably 0.0005 mass% or more and 1 mass% or less, and still more preferably 0.001 mass% or more and 0.5 mass% or less.

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 range is preferable in terms of exhibiting good luminescence.

In the composition of the embodiment containing the essential components of the component (1), the component (2) and the component (4 '), the total content of the component (1), the component (2) and the component (4') is 90% by mass or more based on the total mass of the composition, and the content of the component (2) based on the total mass of the composition is not particularly limited as long as the effect of the present invention is obtained. In the present embodiment, the content ratio of the component (2) to the total mass of the composition is preferably 50% by mass or less, more preferably 10% by mass or less, and still more preferably 5% by mass or less, from the viewpoint of stably dispersing the component (1) in the component (4').

In a composition in which a plurality of perovskite compounds are mixed, the content ratio of the component (2) to the total mass of the composition is preferably 0.001 mass% or more, more preferably 0.01 mass% or more, and even more preferably 0.1 mass% or more, from the viewpoint of maintaining the inherent luminescence wavelength of each perovskite compound.

The above upper limit value and lower limit value may be arbitrarily combined.

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

In the composition of the present embodiment, a composition in which the content ratio of the component (2) to the total mass of the composition is within the above range is preferable from the viewpoint of stably dispersing the component (1) in the component (4') and from the viewpoint of maintaining the inherent luminescence wavelength of each perovskite compound in a composition in which a plurality of perovskite compounds are mixed.

In the composition of the embodiment containing the essential components of the component (1), the component (2) and the component (4 '), the total content ratio of the component (1), the component (2) and the component (4') is 90% by mass or more based on the total mass of the composition, and the total content ratio of the component (1) and the component (2) is not particularly limited based on the total mass of the composition. In the present embodiment, the total content ratio of the component (1) and the component (2) is preferably 60% by mass or less, more preferably 40% by mass or less, further preferably 30% by mass or less, and particularly preferably 20% by mass or less, relative to the total mass of the composition, from the viewpoint of making the component (1) less likely to aggregate and the viewpoint of preventing concentration quenching. From the viewpoint of obtaining a good quantum yield, the amount is preferably 0.0002 mass% or more, more preferably 0.002 mass% or more, and still more preferably 0.005 mass% or more.

The above upper limit value and lower limit value may be arbitrarily combined.

In the composition of the present embodiment, a composition in which the total content ratio of the component (1) and the component (2) with respect to the total mass of the composition is within the above range is preferable from the viewpoint of exhibiting light emission well.

Hereinafter, the composition of the present invention will be described in embodiments.

< ingredient (1) >

(1) The component (A) is a compound having a perovskite crystal structure containing A, B and X as constituent components. Hereinafter, the perovskite compound is described as "perovskite compound". Hereinafter, the component (1) will be described.

The perovskite compound contained in the composition of the present embodiment is a perovskite compound having a, B, and X as constituent components.

The perovskite compound containing a, B, and X as constituent components is not particularly limited as long as the effect of the present invention is obtained, and may be a compound having any one 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 defined as ABX _(3+δ) And (4) showing.

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

Here, δ is a number that can be appropriately changed in accordance with the charge balance of B, and is from-0.7 to 0.7.

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

ABX _(3+δ) (-0.7≦δ≦0.7)…(1)

X represents a component located at each vertex of an octahedron centering on B in the perovskite crystal structure, and is 1 or more anions selected from halide ions and thiocyanate ions.

[A]

In the perovskite compound, 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.

Examples of the cation having a valence of 1 include cesium ion, organic ammonium ion, and amidinium ion. When A in the perovskite compound is cesium ion, an organic ammonium ion having 3 or less carbon atoms, or an amidinium ion having 3 or less carbon atoms, the perovskite compound generally has ABX _(3+δ) The three-dimensional structure of the representation.

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).

[ solution 1]

In the general formula (A3), R ⁶ ～R ⁹ Each independently represents 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 ～R ⁹ Not both as hydrogen atoms.

R ⁶ ～R ⁹ Each of the alkyl groups may be independently linear or branched, and may have an amino group as a substituent.

R ⁶ ～R ⁹ In the case of an alkyl group, 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 of each other.

From R ⁶ ～R ⁹ The cycloalkyl groups represented by the above formulae may each independently have an alkyl group as a substituent, or may have an amino group as a substituent.

R ⁶ ～R ⁹ The number of carbon atoms of the cycloalkyl group is usually 3 to 30, preferably 3 to 11, and more preferably 3 to 8. Number of carbon atoms also including the carbon atom of the substituentThe number of children.

As R ⁶ ～R ⁹ The groups shown are preferably each independently a hydrogen atom or an alkyl group.

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

When the number of carbon atoms of the alkyl group or the cycloalkyl group is 4 or more, a compound having a two-dimensional and/or quasi-two-dimensional (quasi-2D) perovskite crystal structure can be obtained in part or in whole. The two-dimensional perovskite crystal structure is equivalent to the three-dimensional perovskite crystal structure if it is stacked without limitation (references: P.P.Boix et al, J.Phys.chem.Lett.2015, 6, 898-907, etc.).

From R ⁶ ～R ⁹ The total number of carbon atoms contained in the alkyl group represented by R is preferably 1 to 4 ⁶ ～R ⁹ The total number of carbon atoms contained in the cycloalkyl group is preferably 3 to 4. More preferably R ⁶ ～R ⁹ Wherein 1 is an alkyl group having 1 to 3 carbon atoms, R ⁶ ～R ⁹ 3 of which are hydrogen atoms.

As R ⁶ ～R ⁹ Examples of the alkyl group of (b) include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a n-pentyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, a 1-methylbutyl group, a n-hexyl group, a 2-methylpentyl group, a 3-methylpentyl group, a2, 2-dimethylbutyl group, a2, 3-dimethylbutyl group, a n-heptyl group, a 2-methylhexyl group, a 3-methylhexyl group, a2, 2-dimethylpentyl group, a2, 3-dimethylpentyl group, a2, 4-dimethylpentyl group, a3, 3-dimethylpentyl group, a 3-ethylpentyl group, a2, 3-trimethylbutyl group, a n-octyl group, an isooctyl group, a 2-ethylhexyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group and an eicosyl group.

As R ⁶ ～R ⁹ The cycloalkyl group of (A) may be each independently R ⁶ ～R ⁹ Examples of the alkyl group in (1) include an alkyl group having 3 or more carbon atomsExamples of the cycloalkyl group in which a ring is formed include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, norbornyl, isobornyl, 1-adamantyl, 2-adamantyl and tricyclodecyl.

As the organic ammonium ion represented by A, CH is preferable ₃ NH ₃ ⁺ (also referred to as methylammonium ion), C ₂ H ₅ NH ₃ ⁺ (also known as ethylammonium ion.) or C ₃ H ₇ NH ₃ ⁺ (also referred to as propylammonium ion.), more preferably CH ₃ NH ₃ ⁺ Or C ₂ H ₅ NH ₃ ⁺ Further, CH is preferable ₃ NH ₃ ⁺ 。

Examples of the amidinium ion represented by A include an amidinium ion 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 ～R ¹³ Each independently represents 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.

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

From R ¹⁰ ～R ¹³ The number of carbon atoms of the alkyl group is usually 1 to 20, preferably 1 to 4, and more preferably 1 to 3.

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

From R ¹⁰ ～R ¹³ The number of carbon atoms of the cycloalkyl group represented by (a) is usually 3 to 30, preferably 3 to 11, and more preferably 3 to 8. The number of carbon atoms includes the number of carbon atoms of the substituent.

As R ¹⁰ ～R ¹³ Specific examples of the alkyl group of (1) may be each independentlyTo cite R ⁶ ～R ⁹ The alkyl group exemplified in (1).

As R ¹⁰ ～R ¹³ Specific examples of the cycloalkyl group of (1) include R and R independently ⁶ ～R ⁹ Cycloalkyl groups exemplified in (1).

As a group R ¹⁰ ～R ¹³ The groups represented 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 of the alkyl groups and cycloalkyl groups, a perovskite compound having a three-dimensional structure with high emission intensity can be obtained.

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

[B]

In the perovskite compound, B is a component located at the center of a hexahedron having a at the apex and an octahedron having X at the apex in the perovskite crystal structure, and is a metal ion. The metal ion of component B may be a metal ion composed of 1 or more species selected from the group consisting of a metal ion having a valence of 1, a metal ion having a valence of 2, and a metal ion having a valence of 3. B preferably contains a metal ion having a valence of 2, and more preferably contains 1 or more metal ions selected from lead and tin.

[X]

In the perovskite compound, X represents a component located at each vertex of an octahedron centering on B in the perovskite crystal structure, and represents at least 1 anion selected from a halide ion and a thiocyanate ion. 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 may be appropriately selected depending on the desired light emission wavelength, and for example, X may contain bromide ion.

When X is 2 or more types of halide ions, the content ratio of the halide ions may be appropriately selected according to the emission wavelength, and for example, may be a combination of bromide ions and chloride ions, or a combination of bromide ions and iodide ions.

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

When the perovskite compound has a two-dimensional structure, B is the center, X is the vertex, and BX is the center ₆ The octahedrons shown share the X of 4 vertices of the same plane, thereby forming a BX connected by two dimensions ₆ The constituent layers and the layer consisting of A are alternately stacked.

B is a metal cation which can be octahedrally coordinated with respect to X.

In the present specification, the perovskite structure can be confirmed by an X-ray diffraction pattern.

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

In the case of a compound having a perovskite crystal structure having the two-dimensional structure, it is more preferable that a peak derived from (hkl) = (002) is generally observed at a position of 2 θ =1 to 10 ° and a peak derived from (hkl) = (002) is observed at a position of 2 θ =2 to 8 ° in an X-ray diffraction pattern.

As perovskite compounds, from ABX _(3+δ) As specific examples of the compounds having a three-dimensional perovskite crystal structure, CH is preferably exemplified 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) And so on.

As an aspect of the invention, as the perovskite compound, as ABX _(3+δ) The compound having a perovskite-type crystal structure represented by the formula CsPbBr ₃ 、CsPbBr _(3-y) I _y (0<y<3)。

As the perovskite compound, from ₂ BX _(4+δ) Specific examples of the compounds having a two-dimensional perovskite crystal structure are preferably (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) And the like.

Luminescence spectrum

Perovskite compounds are luminophores capable of emitting fluorescence in the visible wavelength region.

When X is bromide ion, the perovskite compound can emit fluorescence having a maximum emission intensity peak in a wavelength region of usually 480nm or more, preferably 500nm or more, more preferably 510nm or more, and usually 700nm or less, preferably 600nm or less, more preferably 580nm or less.

The above upper limit value and lower limit value may be arbitrarily combined.

In another aspect of the present invention, when X is bromide ion, the perovskite compound can emit fluorescence having a maximum emission intensity peak in a wavelength region of usually 480nm to 700nm, preferably 500nm to 600nm, more preferably 510nm to 580 nm.

When X is an iodide ion, the perovskite compound can emit fluorescence having a maximum emission intensity peak in a wavelength range of usually 520nm or more, preferably 530nm or more, more preferably 540nm or more, and usually 800nm or less, preferably 750nm or less, more preferably 730nm or less.

The above upper and lower limits may be arbitrarily combined.

In another aspect of the present invention, when X is an iodide ion, the perovskite compound can emit fluorescence having a maximum emission intensity peak in a wavelength region of usually 520nm to 800nm, preferably 530nm to 750nm, and more preferably 540nm to 730 nm.

When X is a chloride ion, the perovskite compound can emit fluorescence having a maximum emission intensity peak in a wavelength range of usually 300nm or more, preferably 310nm or more, more preferably 330nm or more, and usually 600nm or less, preferably 580nm or less, more preferably 550nm or less.

The above upper limit value and lower limit value may be arbitrarily combined.

In another aspect of the present invention, when X is a chloride ion, the perovskite compound can emit fluorescence having a maximum emission intensity peak in a wavelength region of usually 300nm or more and 600nm, preferably 310nm or more and 580nm or less, and more preferably 330nm or more and 550nm or less.

The average particle size of the component (1) contained in the composition of the present embodiment is not particularly limited as long as the effect of the present invention is obtained. In the composition of the present embodiment, the average particle diameter is preferably 1nm or more, more preferably 2nm or more, and still more preferably 3nm or more, from the viewpoint of maintaining the crystal structure of the component (1) well. 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 500nm or less, from the viewpoint that the component (1) is less likely to sediment.

The above upper limit value and lower limit value may be arbitrarily combined.

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

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

The median particle diameter (D) of the component (1) contained in the composition of the present embodiment ₅₀ ) The present invention 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 that the crystal structure of the component (1) is favorably maintained, the median particle diameter (D) of the component (1) ₅₀ ) Preferably 3nm or more, more preferably 4nm or more, and still more preferably 5nm or more. In the composition of the present embodiment, the median particle diameter (D) of component (1) is small in view of the difficulty in settling of component (1) ₅₀ ) Preferably 5 μm or less, more preferably 500nm or less, and still more preferably 100nm or less.

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

In the present specification, the median particle diameter of the component (1) contained in the composition can be measured by, for example, TEM or SEM. Specifically, the Ferrett diameters of 20 (1) components contained in the composition can be observed by TEM or SEM, and the median diameter (D) can be determined from the distribution thereof ₅₀ )。

< (1) -1 component >

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

In one aspect of the present invention, the difference between the emission peak wavelength of the component (1) -1 and the emission peak wavelength of the component (1) measured under the following conditions is preferably 70nm to 140nm, more preferably 75nm to 135nm, and particularly preferably 80nm to 130 nm.

Measurement conditions

(1) The emission spectra of the component (1) and the component (1) -1 can be measured under conditions of excitation light of 450nm at room temperature and under atmospheric conditions using an absolute PL quantum yield measuring apparatus (for example, "C9920-02" manufactured by Hamamatsu photonics corporation).

< ingredient (2) >

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

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

Here, the anionic group means a group capable of forming a group having a negative charge or a group having a negative charge, and the cationic group means a group capable of forming a group having a positive charge or a group having a positive charge.

In the addition polymerizable compound having an ionic group, examples of the anionic group include-PO ₄ ^2- The group shown, -OSO ₃ ^- A group shown as, -COO ^- The group shown, preferably-OSO ₃ ^- A group shown as, -COO ^- The group shown, more preferably-COO ^- The radicals shown.

In the addition polymerizable compound 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 include an ammonium group and a primary amino group.

In the addition polymerizable compound having an ionic group, the ionic group may be 1 kind or may contain 2 or more kinds.

The addition polymerizable compound having an ionic group may form a salt, and the counter cation in the anionic group is not particularly limited, and preferable examples thereof include an alkali metal cation, an alkaline earth metal cation, and an ammonium cation.

The counter anion in the cationic group is not particularly limited, and may include Br ^- 、Cl ^- 、I ^- 、F ^- Halide ions, carboxylate anions of (a).

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

Examples of the addition polymerization include polymerization of a terminal double bond or triple bond in a compound, and ring-opening polymerization of a cyclic compound. Among the addition polymerizable compounds having an ionic group, the addition polymerizable compound is preferably an ionic polymerizable compound having an ionic group or a radical polymerizable compound having an ionic group that is polymerized by radical polymerization, and more preferably a radical polymerizable compound having an ionic group.

(radical polymerizable Compound having Ionic group)

In the addition polymerizable compound having an ionic group, the radical polymerizable compound having an ionic group is a compound having an ionic group and being polymerized by a reaction of a radical with a polymerizable functional group, and examples of the polymerizable functional group reacting with a radical include a vinyl group and a vinyl group having a substituent, and examples of the polymerizable functional group reacting with a radical include a styrene group, a propylene group, a methylpropylene group, an allyl group, and the like, and may include a propylene group, a styrene group, a methylpropylene group, and a styrene group, and a methylpropylene group.

Among the addition polymerizable compounds having an ionic group, examples of the radical polymerizable compound include compounds having an ionic group such as acrylates and derivatives thereof, methacrylates and derivatives thereof, styrenes and derivatives thereof, acrylonitriles and derivatives thereof, allyl esters and derivatives thereof of organic carboxylic acids, vinyl esters and derivatives thereof of organic carboxylic acids, dialkyl esters and derivatives thereof of fumaric acid, dialkyl esters and derivatives thereof of maleic acid, dialkyl esters and derivatives thereof of itaconic acid, N-vinylamide derivatives of organic carboxylic acids, maleimide and derivatives thereof, and terminally unsaturated hydrocarbons and derivatives thereof.

Examples of the acrylic esters having an ionic group and derivatives thereof include compounds having an ionic group in a part of their structures, such as methyl acrylate, ethyl acrylate, N-propyl acrylate, isopropyl acrylate, N-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, isobornyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 2-hydroxyphenyl acrylate, N-dimethylacrylamide, N-diethylacrylamide, and N-acryloylmorpholine.

Examples of the methacrylate ester having an ionic group and a derivative thereof include compounds having an ionic group in a part of their structures, such as methyl methacrylate, ethyl methacrylate, N-propyl methacrylate, isopropyl methacrylate, N-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate, isobornyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 2-hydroxyphenyl ethyl methacrylate, N-dimethyl methacrylamide, N-diethyl methacrylamide, and N-acryloyl morpholine.

Examples of the styrene having an ionic group and its derivative include styrene, 2, 4-dimethyl-. Alpha. -methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2, 4-dimethylstyrene, 2, 5-dimethylstyrene, 2, 6-dimethylstyrene, 3, 4-dimethylstyrene, 3, 5-dimethylstyrene, 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, 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 -ethylstyrene, α -chlorostyrene, diisopropylbenzene, 4-aminostyrene and the like.

As the acrylonitrile having an ionic group and its derivative, acrylonitrile having an ionic group in a part of the structure such as acrylonitrile can be mentioned. Examples of methacrylonitrile having an ionic group and its derivatives include compounds having an ionic group in a part of the structure of methacrylonitrile and the like.

Examples of the vinyl ester of an organic carboxylic acid having an ionic group and a derivative thereof include compounds having an ionic group in a part of the structure, such as vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl benzoate.

Examples of allyl esters of organic carboxylic acids having an ionic group and derivatives thereof include compounds having an ionic group in a part of the structure such as allyl acetate and allyl benzoate.

Examples of the dialkyl ester of fumaric acid having an ionic group and a derivative thereof include compounds having an ionic group in a part of their structures, such as dimethyl fumarate, diethyl fumarate, diisopropyl fumarate, di-sec-butyl fumarate, diisobutyl fumarate, di-n-butyl fumarate, di-2-ethylhexyl fumarate, and dibenzyl fumarate.

Examples of the dialkyl ester of maleic acid having an ionic group and the derivative thereof include compounds having an ionic group in a part of the structure thereof such as dimethyl maleate, diethyl maleate, diisopropyl maleate, di-sec-butyl maleate, diisobutyl maleate, di-n-butyl maleate, di-2-ethylhexyl maleate, dibenzyl maleate and the like.

Examples of the dialkyl ester of itaconic acid and a derivative thereof having an ionic group include compounds having an ionic group in a part of the structure thereof, such as dimethyl itaconate, diethyl itaconate, diisopropyl itaconate, di-sec-butyl itaconate, diisobutyl itaconate, di-n-butyl itaconate, di-2-ethylhexyl itaconate, and dibenzyl itaconate.

Examples of the N-vinylamide derivative of an organic carboxylic acid having an ionic group include compounds having an ionic group in a part of the structure, such as N-methyl-N-vinylacetamide.

Examples of the maleimide having an ionic group and its derivative include compounds having an ionic group in a part of their structures, such as N-phenylmaleimide and N-cyclohexylmaleimide.

Examples of the terminal unsaturated hydrocarbon having an ionic group and a derivative thereof include compounds having an ionic group in a part of the structure thereof, such as 1-butene, 1-pentene, 1-hexene, 1-octene, vinylcyclohexane, vinyl chloride, and allyl alcohol.

Among the addition polymerizable compounds having an ionic group, examples of the radical polymerizable compound having an ionic group include a compound in which a part of hydrogen atoms of the radical polymerizable compound is substituted with the anionic group, and a compound in which a part of carbon atoms of the radical polymerizable compound is substituted with the anionic group.

(Ionic polymerizable Compound having Ionic group)

In the addition polymerizable compound having an ionic group, the ionic polymerizable compound having an ionic group is a compound having an ionic group and being polymerized by reacting with a polymerizable functional group by cation, anion, or the like, and examples of the polymerizable functional group reacting with an ion include an epoxy group and a vinyl group. Examples of the ionic polymerizable compound having an ionic group include acrylates and derivatives thereof, methacrylates and derivatives thereof, styrenes and derivatives thereof, acrylonitrile and derivatives thereof, allyl esters of organic carboxylic acids and derivatives thereof, vinyl esters of organic carboxylic acids and derivatives thereof, dialkyl esters of fumaric acid and derivatives thereof, dialkyl esters of maleic acid and derivatives thereof, dialkyl esters of itaconic acid and derivatives thereof, N-vinyl amide derivatives of organic carboxylic acids, maleimide and derivatives thereof, terminally unsaturated hydrocarbons and derivatives thereof, and compounds having an ionic group in a part of the structure of an epoxy monomer.

In the addition polymerizable compound having an ionic group, examples of the ionic polymerizable compound having an ionic group include a compound in which a part of a hydrogen atom of the ionic polymerizable compound is substituted with the anionic group, and a compound in which a part of a carbon atom of the ionic polymerizable compound is substituted with the anionic group.

A part or all of the 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.

Examples of the addition polymerizable compound having an ionic group or the salt having a counter cation include barium acrylate, potassium 3-sulfopropylmethacrylate, 3- [ [2- (methacryloyloxy) ethyl ] dimethylammonium ] propionate, 2- (methacryloyloxy) ethyl 2- (trimethylamino) ethyl phosphate, 2-acrylamido-2-methylpropanesulfonic acid, sodium vinylsulfonate, vinylsulfonic acid, sodium p-styrenesulfonate hydrate, sodium 4-vinylbenzenesulfinate, 4-carboxyphenylethene, 3-allyloxypropionic acid, acrylic acid, methacrylic acid, 2-acrylamido-2-methylpropanesulfonic acid, 4-carboxyphenylethene, 3- [ [2- (methacryloyloxy) ethyl ] dimethylammonium ] propionate, methacrylic acid, 2-acrylamido-2-methylpropanesulfonic acid, 4-carboxyphenylethene, 3- [ [ -2- (methacryloyloxy) ethyl ] dimethylammonium ] propionate, methacrylic acid, 4-carboxyphenylethene, 3- [ [2- (methacryloyloxy) ethyl ] dimethylammonium ] propionate, and methacrylic acid, 4-carboxyethylacryloxy ] ethyl ] ammonium propionate.

Among the addition polymerizable compounds having an ionic group, examples of the polymerizable compound having a cationic group or the salt having a counter anion include trimethyl-2-methacryloyloxyethylammonium chloride, 2- (methacryloyloxy) ethyl 2- (trimethylamino) ethylphosphate, 3- [ [2- (methacryloyloxy) ethyl ] dimethylammonium ] propionate, (3-acrylamidopropyl) trimethylammonium chloride, trimethylvinylammonium bromide, 4-vinylbenzylamine, 3-aminopropene hydrochloride, glycidyltrimethylammonium chloride, and also 4-vinylbenzylamine and 3- [ [2- (methacryloyloxy) ethyl ] dimethylammonium ] propionate.

The 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 addition polymerizable compound having an ionic group, which is polymerized by a method described later.

The polymerization refers to a process in which at least a part of polymerizable functional groups such as vinyl group, acryloyl group, methacryloyl group, allyl group, and epoxy group contained in an addition polymerizable compound having an ionic group reacts with a radical or ion generated from a polymerization initiator or the like to form a polymer.

Examples of the polymer of the addition polymerizable compound having an ionic group include a polystyrene resin, a polyvinyl resin, a polyacrylic resin, a polymethacrylic resin, a polyallyl resin, and an epoxy resin, which contain at least 1 ionic group.

< ingredient (3) >

(3) The component (A) is a solvent. The solvent is not particularly limited as long as it is a medium capable of dispersing the component (1), and is preferably a solvent in which the component (1) is hardly dissolved.

In the present specification, the term "solvent" means a substance that is in a liquid state at 25 ℃ under 1 atmosphere (excluding polymerizable compounds and polymers).

In the present specification, "dispersion" means that the component (1), the aggregate, and the like are suspended or suspended in a solvent, a polymerizable compound, a polymer, and the like, and may be partially precipitated.

Examples of the solvent include esters such as methyl formate, ethyl formate, propyl formate, pentyl formate, methyl acetate, ethyl acetate, and pentyl acetate; ketones such as γ -butyrolactone, acetone, dimethyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, and methylcyclohexanone; ethers such as diethyl ether, methyl tert-butyl ether, diisopropyl ether, dimethoxymethane, dimethoxyethane, 1, 4-dioxane, 1, 3-dioxolane, 4-methyldioxolane, tetrahydrofuran, methyltetrahydrofuran, anisole and phenetole; alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, t-butanol, 1-pentanol, 2-methyl-2-butanol, methoxypropanol, diacetone alcohol, cyclohexanol, 2-fluoroethanol, 2-trifluoroethanol, and 2, 3-tetrafluoro-1-propanol; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, and triethylene glycol dimethyl ether; amide group-containing organic solvents such as N-methyl-2-pyrrolidone, N-dimethylformamide, acetamide, and N, N-dimethylacetamide; organic solvents having a nitrile group such as acetonitrile, isobutyronitrile, propionitrile, and methoxyacetonitrile; organic solvents having a carbonate group such as ethylene carbonate and propylene carbonate; organic solvents having halogenated hydrocarbon groups such as methylene chloride and chloroform; organic solvents having hydrocarbon groups such as n-pentane, cyclohexane, n-hexane, benzene, toluene, and xylene; dimethylsulfoxide, 1-octadecene, etc.

Among them, methyl formate, ethyl formate, propyl formate, pentyl formate, methyl acetate, ethyl acetate, pentyl acetate and other esters; ketones such as γ -butyrolactone, acetone, dimethyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, and methylcyclohexanone; ethers such as diethyl ether, methyl tert-butyl ether, diisopropyl ether, dimethoxymethane, dimethoxyethane, 1, 4-dioxane, 1, 3-dioxolane, 4-methyldioxolane, tetrahydrofuran, methyltetrahydrofuran, anisole, and phenetole; organic solvents having a nitrile group such as acetonitrile, isobutyronitrile, propionitrile, and methoxyacetonitrile; organic solvents having a carbonate group such as ethylene carbonate and propylene carbonate; organic solvents having halogenated hydrocarbon groups such as methylene chloride and chloroform; organic solvents having hydrocarbon groups such as n-pentane, cyclohexane, n-hexane, benzene, toluene, and xylene, preferably organic solvents having halogenated hydrocarbon groups such as methylene chloride and chloroform, in view of low polarity and difficulty in dissolving the component (1); an organic solvent having a hydrocarbon group such as n-pentane, cyclohexane, n-hexane, benzene, toluene, or xylene.

< ingredient (4) >

(4) The component (C) is a polymerizable compound or polymer other than the component (2).

The polymerizable compound other than the component (2) is a polymerizable compound having no ionic group.

The polymerizable compound other than the component (2) contained in the composition of the present embodiment is not particularly limited as long as it has the effect of the present invention, and may be one or two. The polymerizable compound is preferably a polymerizable compound having low solubility of the component (1) at the temperature for producing the composition of the present embodiment.

In the present specification, the "polymerizable compound" refers to a compound of a monomer having a polymerizable group.

For example, when the composition of the present embodiment is produced at room temperature and normal pressure, the polymerizable compound other than the component (2) is not particularly limited, and examples thereof include known polymerizable compounds other than the component (2), such as styrene, acrylic acid ester, methacrylic acid ester, and acrylonitrile. Among these, as the polymerizable compound other than the component (2), either one or both of an acrylate and a methacrylate as monomer components of the acrylic resin are preferable.

The polymer other than the component (2) contained in the composition of the present embodiment is not particularly limited, and may be one or two. The polymer is preferably a polymer having low solubility of the component (1) at the temperature for producing the composition of the present embodiment.

For example, when the composition of the present embodiment is produced at room temperature and normal pressure, the polymer other than the component (2) is not particularly limited, and examples thereof include known polymers such as polystyrene, acrylic resins, and epoxy resins. Among them, acrylic resins are preferable as the polymer. The acrylic resin contains a structural unit derived from either or both of an acrylate and a methacrylate.

In the composition of the present embodiment, when either or both of the acrylate and the methacrylate and the structural unit derived therefrom are expressed in mol% based on the total structural units contained in the polymerizable compound or the polymer of component (4), they 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 to 1200,000, more preferably 1,000 to 800,000, and still more preferably 5,000 to 150,000.

In the present specification, "weight average molecular weight" refers to a polystyrene equivalent value measured by a Gel Permeation Chromatography (GPC) method.

< ingredient (5) >

(5) Ingredient is at least 1 compound or ion selected from ammonia, amines and carboxylic acids, and salts or ions thereof.

Examples of the component (5) include ammonia, amines, and carboxylic acids, and at least 1 compound or ion selected from these salts or ions in the form obtainable as the above-mentioned compound.

That is, the component (5) includes at least 1 compound or ion selected from ammonia, amine, carboxylic acid, a salt of ammonia, a salt of amine, a salt of carboxylic acid, an ion of ammonia, an ion of amine, and an ion of carboxylic acid.

Ammonia, amines and carboxylic acids, and their salts or ions, generally function as capped ligands. The "capping ligand" is a compound having an action of adsorbing to the surface of the component (1) to stably disperse the component (1) in the composition. Examples of the ions or salts (ammonium salts and the like) of ammonia or amine include ammonium cations represented by the general formula (A1) described later and ammonium salts containing the ammonium cations. Examples of the ion or salt (e.g., carboxylate salt) of the carboxylic acid include a carboxylate anion represented by the general formula (A2) described below and a carboxylate salt containing the same. The composition of the present embodiment may contain either or both of an ammonium salt and a carboxylate.

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

[ solution 2]

In the general formula (A1), R ¹ ～R ³ Represents a hydrogen atom, R ⁴ Represents a hydrogen atom or a 1-valent hydrocarbon group. R is ⁴ The hydrocarbyl groups represented may be saturated hydrocarbyl groups (i.e., alkyl or cycloalkyl) or unsaturated hydrocarbyl groups.

R ⁴ The alkyl group may be linear or branched.

R ⁴ The alkyl group represented has a carbon number of usually 1 to 20, preferably 5 to 20, and more preferably 8 to 20.

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

R ⁴ The unsaturated hydrocarbon group(s) may be linear or branched.

R ⁴ The unsaturated hydrocarbon group (2) has usually 2 to 20 carbon atoms, preferably 5 to 20 carbon atoms, and more preferably 8 to 20 carbon atoms.

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

As R ⁴ Specific examples of the alkyl group of (1) include R ⁶ ～R ⁹ The alkyl groups exemplified in (1).

As R ⁴ Specific examples of the cycloalkyl group of (1) include R ⁶ ～R ⁹ Cycloalkyl groups exemplified in (1).

As R ⁴ The alkenyl group of (1) can be exemplified by R ⁶ ～R ⁹ The above-mentioned linear or branched alkyl group as exemplified in (1) is an alkenyl group in which a single bond (C — C) between any carbon atoms is substituted with a double bond (C = C), and the position of the double bond is not limited.

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

When the ammonium cation forms a salt, the counter anion is not particularly limited, and a preferable example thereof is Br ^- 、Cl ^- 、I ^- 、F ^- Halide ions, carboxylate ions, and the like.

Preferred examples of the ammonium salt having the ammonium cation represented by the general formula (A1) and the counter anion include n-octylammonium salt and oleylammonium salt.

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

R ⁵ ―CO ₂ ^- ···(A2)

In the general formula (A2), R ⁵ Represents a monovalent hydrocarbon group. R is ⁵ The hydrocarbyl group represented may be a saturated hydrocarbyl group (i.e., alkyl group, cycloalkyl group), or an unsaturated hydrocarbyl group.

R ⁵ The alkyl group may be linear or branched. R ⁵ The alkyl group represented has a carbon number of usually 1 to 20, preferably 5 to 20, and more preferably 8 to 20.

From R ⁵ The cycloalkyl group represented may have an alkyl group as a substituent. The number of carbon atoms of the cycloalkyl group is usually 3 to 30, preferably 3 to 20, and more preferably 3 to 203 to 11. The number of carbon atoms also includes the number of carbon atoms of the substituent.

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

R ⁵ The unsaturated hydrocarbon group represented by (a) has usually 2 to 20 carbon atoms, preferably 5 to 20 carbon atoms, and more preferably 8 to 20 carbon atoms.

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

As R ⁵ Specific examples of the alkyl group of (1) include R ⁶ ～R ⁹ The alkyl group exemplified in (1).

As R ⁵ Specific examples of the cycloalkyl group of (1) include R ⁶ ～R ⁹ Cycloalkyl groups exemplified in (1).

As R ⁵ Specific examples of the alkenyl group of (1) include R ⁴ Alkenyl groups exemplified in (1).

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

When the carboxylate anion forms a salt, the counter cation is not particularly limited, and preferable examples thereof include an alkali metal cation, an alkaline earth metal cation, and an ammonium cation.

< ingredient (6) >

(6) The component (C) is at least 1 compound selected from the group consisting of organic compounds having an amino group, an alkoxy group and a silicon atom, silazanes and modified silazanes thereof, and the like.

(organic Compound having amino group, alkoxy group and silicon atom)

The composition of the present invention may comprise an organic compound having an amino group, an alkoxy group and a silicon atom.

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.

[ solution 3]

In the general formula (A5-5), A is 2-valent hydrocarbon group, O is oxygen atom, N is nitrogen atom, si is silicon atom, R ²² ～R ²³ Each independently represents a hydrogen atom, an alkyl group or a cycloalkyl group, R ²⁴ Represents alkyl or cycloalkyl, R ²⁵ ～R ²⁶ Represents a hydrogen atom, an alkyl group, an alkoxy group or a cycloalkyl group.

As R ²² ～R ²⁶ The alkyl group (2) may be linear or branched.

The alkyl group has usually 1 to 20 carbon atoms, preferably 5 to 20 carbon atoms, and more preferably 8 to 20 carbon atoms.

As R ²² ～R ²⁶ The cycloalkyl group of (b) may have an alkyl group as a substituent. The cycloalkyl group has usually 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms, and more preferably 3 to 11 carbon atoms. The number of carbon atoms includes the number of carbon atoms of the substituent.

As R ²² ～R ²⁶ Specific examples of the alkyl group of (1) include R ⁶ ～R ⁹ The alkyl group exemplified in (1).

As R ²² ～R ²⁶ Specific examples of the cycloalkyl group of (1) include R ⁶ ～R ⁹ Cycloalkyl groups exemplified in (1).

As R ²⁵ ～R ²⁶ Alkoxy of (2) can be exemplified by R ⁶ ～R ⁹ Examples of the above-mentioned linear or branched alkyl group include a group having a valence of 1 in which an oxygen atom is bonded.

As R ²⁵ ～R ²⁶ Examples of the alkoxy group of (b) include methoxy, ethoxy and butoxy, and methoxy is preferred.

The 2-valent hydrocarbon group represented by a may be a group obtained by removing 2 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 of the alkylene group is usually 1 to 100, preferably 1 to 20, and more preferably 1 to 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.

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

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

(silazane or its modification)

The compositions of the invention may contain silazanes or modifications thereof.

Silazanes are compounds having Si-N-Si bonds.

The silazane may be linear, branched or cyclic. The silazane may be a low-molecular or high-molecular silazane (which may be referred to as polysilazane in this specification).

In the present specification, "low-molecular silazane" means a silazane having a number average molecular weight of less than 600, and "high-molecular silazane (polysilazane)" means a silazane having a number average molecular weight of 600 to 2000.

In the present specification, "number average molecular weight" refers to a polystyrene equivalent value measured by a Gel Permeation Chromatography (GPC) method.

For example, low-molecular 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 preferable.

The silazane may be modified with silicon oxide by a method described later and then used.

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

Modified means that in at least a part of the Si-N-Si bonds contained in the silazane, N is replaced by O, the modified silazane is a compound containing a Si-O-Si bond.

As modified silazanes, for example, a low-molecular compound in which at least 1N contained in the general formula (B1) or (B2) is substituted with O, a high-molecular compound in which at least 1N contained in polysilazane having a structural unit represented by the general formula (B3) is substituted with O, or a high-molecular compound in which at least 1N contained in polysilazane having a structure represented by the general formula (B4) is substituted with O are preferable.

The proportion of the number of substituted O relative 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 proportion of the number of substituted O 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 proportion of the number of substituted O with respect to the total amount of N contained in general formula (B4) is preferably 0.1 to 99%, more preferably 10 to 97%, and still more preferably 30 to 95%.

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

The number of Si atoms, the number of N atoms, and the number of O atoms contained in the silazane and its modified product can be calculated by nuclear magnetic resonance spectroscopy (NMR), X-ray photoelectron spectroscopy (XPS), energy dispersive X-ray analysis (EDX) using a Transmission Electron Microscope (TEM), or the like.

Particularly preferred is a method of 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 contained in the silazane and its modified product measured by the above method to the number of N atoms 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.

[ solution 4]

In the general formula (B1), R ¹⁴ And R ¹⁵ Each independently represents 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. The alkyl group having 1 to 20 carbon atoms, the alkenyl group having 1 to 20 carbon atoms, the cycloalkyl group having 3 to 20 carbon atoms, the aryl group having 6 to 20 carbon atoms or the alkylsilyl group having 1 to 20 carbon atoms may have a substituent such as an amino group. Plural R ¹⁵ May be the same or different.

As the low-molecular silazane represented by the general formula (B1), mention may be made of 1, 3-divinyl-1, 3-tetramethyldisilazane, 1, 3-diphenyltetramethyldisilazane and 1, 3-hexamethyldisilazane.

[ solution 5]

In the general formula (B2), R ¹⁴ And R ¹⁵ As described above.

Plural R ¹⁴ May be the same or different.

Plural R ¹⁵ May be the same or different.

n represents 1 to 20 inclusive. n may be 1 to 10, or 1 or 2.

As the low-molecular silazane represented by the general formula (B2), octamethylcyclotetrasilazane, 2,4, 6-hexamethylcyclotrisilazane and 2,4, 6-trimethyl-2, 4, 6-trivinylcyclotrisilazane are exemplified.

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

The polysilazane is a polymer compound having a Si — N — Si bond, and is not particularly limited, and examples thereof include a polymer compound having a structural unit represented by the following general formula (B3). The number of the structural units represented by the general formula (B3) contained in the polysilazane may be 1 or more.

[ solution 6]

In the general formula (B3), R ¹⁴ And R ¹⁵ As described above.

Plural R ¹⁴ May be the same or different.

Plural R ¹⁵ May be the same or different.

m represents an integer of 2 to 10000 inclusive.

The polysilazane having a structural unit represented by the general formula (B3) may be, for example, one wherein R ¹⁴ And R ¹⁵ Perhydropolysilazanes which are all hydrogen atoms.

The polysilazane having a structural unit represented by the general formula (B3) may have, for example, at least 1R ¹⁵ An organopolysiloxane which is a group other than a hydrogen atom. The perhydropolysilazane and the organic polysilazane may be appropriately selected depending on the application, and may be used in combination.

The polysilazane may have a ring structure in a part of the molecule, and may have a structure represented by the general formula (B4), for example.

[ solution 7]

n ₂ Represents an integer of 1 to 10000 inclusive. n is ₂ The number of the carbon atoms may be 1 to 10, or 1 or 2.

The silazane or its modified form is not particularly limited, and from the viewpoint of improving dispersibility and suppressing aggregation, an organic polysilazane or its modified form is preferable. The organic polysilazane may be, for example, an organic polysilazane having a structural unit represented by the general formula (B3) wherein R in the general formula (B3) ¹⁴ And R ¹⁵ At least one of the above groups 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, an aryl group having 6 to 20 carbon atoms or an alkylsilyl group having 1 to 20 carbon atoms. Further, it may be an organopolysilazane having a structure represented by the general formula (B4) wherein at least 1 bond in the general formula (B4) is bonded to R ¹⁴ Or R ¹⁵ Bonding of the above R ¹⁴ And R ¹⁵ At least 1 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, an aryl group having 6 to 20 carbon atoms or an alkylsilyl group having 1 to 20 carbon atoms.

The organic polysilazane is preferably an organic polysilazane having a structural unit represented by the general formula (B3) wherein R in the general formula (B3) ¹⁴ And R ¹⁵ At least one of which is a methyl group, or preferably a polysilazane having a structure represented by the general formula (B4) wherein at least one bond in the general formula (B4) is bonded to R ¹⁴ Or R ¹⁵ Is bonded to said R ¹⁴ And R ¹⁵ At least one of which is methyl.

Preferably R ¹⁴ Or R ¹⁵ An organic polysilazane in which at least a part of the component (a) is a methyl group.

Typical polysilazanes are those having a straight-chain structure and a ring structure such as a 6-or 8-membered ring. As described above, the molecular weight is 600 to 2000 (in terms of polystyrene) in terms of number average molecular weight (Mn), and may be liquid or solid depending on the molecular weight. As the polysilazane, commercially available products such as NN120-10, NN120-20, NAX120-20, NN110, NAX120, NAX110, NL120A, NL110A, NL150A, NP110, NP140 (AZ electronic Materials Co., ltd.), AZNN-120-20, durazane (registered trademark) 1500SlowCure, durazane (registered trademark) 1500Rapidcure, durazane (registered trademark) 1800 (Merkerform Materials Co., ltd.), and Durazane (registered trademark) 1033 (Merkerform Materials Co., ltd.) can be used.

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

< blending ratio of respective ingredients >

In the composition of the present embodiment, the mixing ratio of the component (1) and the component (2) may be determined appropriately according to the kind of the component (1) and the component (2) as long as 2 emission peaks can be displayed by the component (2) even when 2 kinds of perovskite compounds are mixed.

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

(1) A composition having a blending ratio of the component (2) and the component (2) within the above range is preferable from the viewpoint that 2 emission peaks are exhibited even when 2 kinds of perovskite compounds are mixed with the component (2).

The blending ratio of the component (1) to the total of the components (3) and (4) in the composition of the present embodiment may be appropriately determined depending on the types of the components (1), (3) and (4) as long as the light-emitting effect of the component (1) can be exhibited well.

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

(1) A composition in which the blending ratio of the component (3) to the total of the components (4) falls within the above range is preferable from the viewpoint that the aggregation of the component (1) is less likely to occur and the light-emitting property is also exhibited favorably.

The present invention provides a composition of an embodiment containing component (1), component (2), component (5), and at least one selected from component (3) and component (4), or a composition of an embodiment containing component (1), component (2), component (4 ') and component (5), wherein the total content ratio of component (1), component (2) and component (4') is 90 mass% or more relative to the total mass of the composition, and the mixing ratio of component (1) and component (5) may be appropriately determined depending on the types of components (1) to (5) as long as the light-emitting effect of component (1) can be exhibited well.

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

(1) A composition in which the blending ratio of the total of the component (1) and the component (5) is within the above range is preferable from the viewpoint that the aggregation of the component (1) is less likely to occur and the light-emitting property is also exhibited favorably.

The present invention provides a composition of an embodiment containing at least one selected from the group consisting of component (1), component (2), component (6), and component (3) and component (4), or a composition of an embodiment containing component (1), component (2), component (4 ') and component (6), wherein the total content ratio of component (1), component (2) and component (4') is 90 mass% or more relative to the total mass of the composition, and the mixing ratio of component (1) and component (6) may be appropriately determined depending on the types of components (1) to (6) as long as the light-emitting effect of component (1) can be exhibited well.

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

(1) A composition in which the total mixing ratio of the component (1) and the component (6) is within the above range is preferable from the viewpoint that the aggregation of the component (1) is less likely to occur and the light-emitting property is also exhibited favorably.

One aspect of the present invention is a composition comprising the component (1), the component (2), and the component (3), wherein CsPbBr is used as the component (1) ₃ The perovskite compound represented by the formula (2), wherein the component (2) is selected from the group consisting of 4-vinylbenzylamine, 4-carboxystyrene, 2-acrylamido-2-methylpropanesulfonic acid, and 3- [ [2- (methacryloyloxy) ethyl ] sulfonic acid]Dimethyl ammonium salt]At least one addition polymerizable compound selected from propionic acid esters and methacrylic acid, wherein the mass ratio of the component (1) to the component (2) is [ (1)/(2)]0.001 to 0.100 of the composition (A).

Another aspect of the present invention is a composition comprising the component (1), the component (2) and the component (3), wherein the component (1) is CsPbBr _(3-y) I _y (0<y<3) The perovskite compound represented by (1), (2) is a polymer of methacrylic acid, and the composition (B) has a mass ratio [ (1)/(2) ] of the component (1) to the component (2) of 0.001 to 0.080.

Another aspect of the present invention is a composition comprising the component (1), the component (2) and the component (4'), wherein CsPbBr is used as the component (1) ₃ The perovskite compound represented by the formula (2), wherein the component (2) is selected from the group consisting of 4-vinylbenzylamine, 4-carboxyphenethylene, 2-acrylamido-2-methylpropanesulfonic acid, and 3- [ [2- (methacryloyloxy) ethyl ] ethyl]Dimethyl ammonium salt]At least one addition polymerizable compound selected from propionic acid esters and methacrylic acid, wherein the mass ratio of the component (1) to the component (2) is [ (1)/(2)]A composition (C) of 0.001 to 0.050.

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

Another aspect of the present invention is a composition comprising the component (1), the component (2), the component (3) and the component (6), wherein CsPbBr is used as the component (1) ₃ The perovskite compound represented by the formula (2), wherein the component (2) is selected from the group consisting of 4-vinylbenzylamine, 4-carboxyphenethylene, 2-acrylamido-2-methylpropanesulfonic acid, and 3- [ [2- (methacryloyloxy) ethyl ] ethyl]Dimethyl ammonium salt]At least one addition polymerizable compound of propionate and methacrylic acidThe polymer of (3), wherein the mass ratio of the component (1) to the component (2) is [ (1)/(2)]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]A composition (D) of 25 to 125.

In the composition (D), the component (2) is particularly preferably 4-vinylbenzylamine or methacrylic acid. In the composition (D), the component (6) is preferably a silazane or a modified silazane, and more preferably a polysilazane or a modified polysilazane.

Another aspect of the present invention is a composition comprising the component (1), the component (2), the component (3) and the component (6), wherein the component (1) is CsPbBr _(3-y) I _y (0<y<3) The perovskite compound represented by the formula (2), wherein the component (2) is selected from the group consisting of 4-vinylbenzylamine, 4-carboxystyrene, 2-acrylamido-2-methylpropanesulfonic acid, and 3- [ [2- (methacryloyloxy) ethyl group]Dimethyl ammonium salt]At least one addition polymerizable compound selected from the group consisting of propionic acid esters and methacrylic acid, wherein the mass ratio of the component (1) to the component (2) is [ (1)/(2)]0.001 to 0.060, the molar ratio of the metal ion of the B component of the perovskite compound to the Si element of the (6) component [ Si/B ]]A composition (E) of 3 to 60.

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

< method for producing composition >

Hereinafter, a method for producing the composition of the present invention will be described with reference to embodiments. According to the method for producing the composition of the present embodiment, the composition of the embodiment of the present invention can be produced. The composition of the present invention is not limited to the composition produced by the method for producing a composition of the following embodiment.

(1) Process for producing perovskite compound containing A, B and X as constituent components

The perovskite compound can be produced by the method of embodiment 1 or embodiment 2 described below with reference to known literatures (Nano lett.2015, 15, 3692-3696, ACSNano, 2015, 9, 4533-4542).

(embodiment 1 of the method for producing a perovskite Compound having A, B and X as Components)

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

Hereinafter, a manufacturing method including the following steps will be described: dissolving a compound containing the component B and the component X and a compound containing the component A or the component A and the 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 solubility of the perovskite compound in the solvent lower than that of the solvent x used in the step of obtaining the solution g.

The solubility refers to the solubility at the temperature at which the mixing step is performed.

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

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

The step of mixing the solution g and the solvent y may be (I) a step of dropping the solution g into the solvent y or (II) a step of dropping the solvent y into the solution g, but is preferably (I) from the viewpoint of improving the dispersibility of the component (1).

From the viewpoint of improving the dispersibility of the component (1), stirring is preferably performed at the time of dropwise addition.

In the step of mixing the solution g and the solvent y, the temperature is not particularly limited, but is preferably in the range of-20 ℃ to 40 ℃ inclusive, more preferably in the range of-5 ℃ to 30 ℃ inclusive, from the viewpoint of ensuring the ease of precipitation of the component (1).

The 2 types of solvents x and y having different solubilities in a solvent of the perovskite compound used in the above production method are not particularly limited, and for example, 2 types selected from the following solvents are exemplified: alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, t-butanol, 1-pentanol, 2-methyl-2-butanol, methoxypropanol, diacetone alcohol, cyclohexanol, 2-fluoroethanol, 2-trifluoroethanol, 2, 3-tetrafluoro-1-propanol; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, and triethylene glycol dimethyl ether; amide group-containing organic solvents such as N-methyl-2-pyrrolidone, N-dimethylformamide, acetamide, and N, N-dimethylacetamide; esters such as methyl formate, ethyl formate, propyl formate, pentyl formate, methyl acetate, ethyl acetate, pentyl acetate; ketones such as γ -butyrolactone, acetone, dimethyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, and methylcyclohexanone; ethers such as diethyl ether, methyl tert-butyl ether, diisopropyl ether, dimethoxymethane, dimethoxyethane, 1, 4-dioxane, 1, 3-dioxolane, 4-methyldioxolane, tetrahydrofuran, methyltetrahydrofuran, anisole, and phenetole; organic solvents having a nitrile group such as acetonitrile, isobutyronitrile, propionitrile, and methoxyacetonitrile; organic solvents having a carbonate group such as ethylene carbonate and propylene carbonate; organic solvents having halogenated hydrocarbon groups such as methylene chloride and chloroform; organic solvents having hydrocarbon groups such as n-pentane, cyclohexane, n-hexane, benzene, toluene, and xylene; dimethyl sulfoxide (DMSO).

The solvent x used in the step of obtaining the solution g in the above production method is preferably a solvent having high solubility of the perovskite compound in the solvent, and examples thereof include alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, t-butanol, 1-pentanol, 2-methyl-2-butanol, methoxypropanol, diacetone alcohol, cyclohexanol, 2-fluoroethanol, 2-trifluoroethanol, and 2, 3-tetrafluoro-1-propanol when the above step is performed at room temperature (10 ℃ to 30 ℃); glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, and triethylene glycol dimethyl ether; amide group-containing organic solvents such as N-methyl-2-pyrrolidone, N-dimethylformamide, acetamide, and N, N-dimethylacetamide; dimethyl sulfoxide (DMSO).

The solvent y used in the mixing step included in the above-mentioned production method is preferably a solvent in which the perovskite compound has low solubility in the solvent, and examples of the solvent y when the above-mentioned step is carried out at room temperature (10 ℃ to 30 ℃) include esters such as methyl formate, ethyl formate, propyl formate, pentyl formate, methyl acetate, ethyl acetate, and pentyl acetate; ketones such as γ -butyrolactone, acetone, dimethyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, and methylcyclohexanone; ethers such as diethyl ether, methyl tert-butyl ether, diisopropyl ether, dimethoxymethane, dimethoxyethane, 1, 4-dioxane, 1, 3-dioxolane, 4-methyldioxolane, tetrahydrofuran, methyltetrahydrofuran, anisole, and phenetole; organic solvents having a nitrile group such as acetonitrile, isobutyronitrile, propionitrile, and methoxyacetonitrile; organic solvents having a carbonate group such as ethylene carbonate and propylene carbonate; organic solvents having halogenated hydrocarbon groups such as methylene chloride and chloroform; and organic solvents having hydrocarbon groups such as n-pentane, cyclohexane, n-hexane, benzene, toluene, and xylene.

Among the 2 solvents having different solubilities, the difference in solubility is preferably (100. Mu.g/100 g solvent) or more (90 g/100g solvent) or less, more preferably (1 mg/100g solvent) or more (90 g/100g solvent) or less. From the viewpoint of making the difference in solubility (100 μ g/100g solvent) or more (90 g/100g solvent) or less, for example, in the case of the step of mixing at room temperature (10 ℃ to 30 ℃ inclusive), it is preferable that the solvent x used in the step of obtaining a solution is an amide group-containing organic solvent such as N, N-dimethylacetamide or dimethylsulfoxide, and the solvent y used in the step of mixing is an organic solvent having a halogenated hydrocarbon group such as dichloromethane or chloroform; an organic solvent having a hydrocarbon group such as n-pentane, cyclohexane, n-hexane, benzene, toluene, or xylene.

As a method of taking out the perovskite compound from the obtained dispersion liquid containing the perovskite compound, there is a method of recovering only the perovskite compound by performing solid-liquid separation.

Examples of the solid-liquid separation method include a method such as filtration and a method using solvent evaporation.

(embodiment 2 of the method for producing a perovskite Compound having A, B and X as Components)

The method for producing a perovskite compound may include a step of dissolving the B component, the X component, and the a component in a high-temperature solvent z to obtain a solution h, and a step of cooling the obtained solution h. More specifically, a production method comprising the steps of: a step of adding a compound containing the component B and the component X and a compound containing the component A, or a compound containing the component A and the component X to a high-temperature solvent z to dissolve them to obtain a solution h; and a step of cooling the obtained solution h.

The step of dissolving the compound containing the component B and the component X and the compound containing the component a or the component a and the component X in the high-temperature solvent z to obtain the solution h may be a step of adding the compound containing the component B and the component X and the compound containing the component a or the component a and the component X to the solvent z, and then raising the temperature to obtain the solution h.

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 a difference in solubility caused by a temperature difference.

The above-mentioned production method preferably includes a step of adding a capping ligand from the viewpoint of stably dispersing the perovskite compound. Preferably, the solution h contains a capping ligand before the cooling step.

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

The high-temperature solvent z is not particularly limited as long as it is a solvent having a temperature at which the compound containing the components B and X and the compound containing the component a or the compound containing the components a and X are dissolved, and is, for example, preferably 60 ℃ to 600 ℃ inclusive, and more preferably 80 ℃ to 400 ℃ inclusive.

The cooling temperature is preferably-20 ℃ to 50 ℃ inclusive, more preferably-10 ℃ to 30 ℃ inclusive.

The cooling rate is preferably 0.1 to 1500 ℃/min, more preferably 10 to 150 ℃/min.

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

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

Examples of the solid-liquid separation method include a method such as filtration, and a method using solvent evaporation.

[ Process for producing a composition containing component (1), (2) and (3) ]

The method for producing the composition containing the component (1), the component (2) and the component (3) may be, for example, the following production method (a 1) or the following production method (a 2).

Production method (a 1): comprises a step of mixing the component (1) and the component (3) and a step of mixing the mixture of the component (1) and the component (3) with the component (2).

Production method (a 2): comprises a step of mixing the component (1) and the component (2), and a step of mixing the mixture of the component (1) and the component (2) with the component (3).

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

In the embodiment, in the case of producing a composition containing a polymer of an addition polymerizable compound having an ionic group, the following production method (a 3) or production method (a 4) can be employed.

Production method (a 3): comprises a step of mixing the component (1) and the component (3), a step of mixing a mixture of the component (1) and the component (3) with the component (2 '), and a step of polymerizing a mixture containing the component (1), the component (2') and the component (3).

Production method (a 4): comprises a step of mixing the component (1) and the component (2 '), a step of mixing a mixture of the component (1) and the component (2 ') with the component (3), and a step of polymerizing a mixture of the component (1), the component (2 ') and the component (3).

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-mentioned production method, stirring is preferably performed from the viewpoint of improving dispersibility.

In the mixing step included in the above-mentioned production method, the temperature is not particularly limited, and from the viewpoint of uniform mixing, the temperature is preferably in the range of 0 ℃ to 100 ℃, and more preferably in the range of 10 ℃ to 80 ℃.

The method for producing the composition is preferably the production method (a 1) or the production method (a 3) from the viewpoint of improving the dispersibility of the component (1).

Method for carrying out polymerization treatment

The method of carrying out the polymerization treatment in the above-mentioned production method is not particularly limited as long as it is a method of forming a polymer by reacting at least a part of the polymerizable functional groups contained in the addition polymerizable compound having an ionic group. Examples of the method for carrying out the polymerization treatment include a known method such as a method of reacting with a polymerization initiator.

The polymerization initiator used in the method using a polymerization initiator may be a known polymerization initiator such as a photopolymerization initiator or a thermal polymerization initiator.

Photopolymerization initiator

Examples of the photopolymerization initiator include photopolymerization initiators generally used in the art, such as ultraviolet rays and visible light.

Photo-radical polymerization initiator

The photo radical polymerization initiator is a polymerization initiator that generates radicals by light such as ultraviolet rays and visible light, and as the photo radical polymerization initiator, as the photo polymerization initiator, examples thereof include acetophenone, 2-dimethoxy-2-phenylacetophenone, 2-diethoxyacetophenone, 4-isopropyl-2-hydroxy-2-methylpropiophenone, 4' -bis (diethylamino) benzophenone, methyl (benzoyl) benzoate, 1-phenyl-1, 2-propanedione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-1, 2-propanedione-2- (benzoyl) oxime, benzoin carbonyl compounds such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin octyl ether, benzil, benzyl dimethyl ketal, benzyl diethyl ketal, and diacetyl, anthraquinones such as methylanthraquinone, chloroanthraquinone, chlorothioxanthone, 2-methylthioxanthone, and 2-isopropylthioxanthone, and sulfur compounds such as diphenyl disulfide and dithiocarbamate.

Photo cation polymerization initiator

The cationic polymerization initiator is not particularly limited as long as it is an initiator that generates an acid by irradiation with a known active energy ray, and examples thereof include sulfonium salts, iodonium salts, phosphonium salts, and pyridinium salts.

Examples thereof include triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, bis (4- (diphenylsulfonium) -phenyl) sulfide-bis (hexafluorophosphate), bis (4- (diphenylsulfonium) -phenyl) sulfide-bis (hexafluoroantimonate), 4-bis (p-tolyl) sulfonium-4' -tert-butylphenyl carbonyl-diphenylsulfonium-hexafluoroantimonate, 7-bis (p-tolyl) sulfonium-2-isopropylthioxanthone hexafluorophosphate, 7-bis (p-tolyl) sulfonium-2-isopropylthioxanthone hexafluoroantimonate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, bis (dodecylphenyl) iodonium tetrakis (pentafluorophenyl) borate, tetrafluorophosphonium hexafluorophosphate, and tetrafluorophosphonium hexafluoroantimonate.

Thermal radical polymerization initiator

<xnotran> , 2,2' - ,2,2 ' - ,2,2 ' - (2,4- ), 4,4' - (4- ), 1,1' - ( ), 2,2' - (2- ), 2,2' - (2- ) 2 , , , , , , ,2,4- , , , ,2,4,4- -2- , , , ; </xnotran> Dialkyl peroxides such as dicumyl peroxide, t-butylcumyl peroxide, di-t-butyl peroxide, and tris (t-butyloxy) triazine; peroxy ketals such as 1, 1-di-tert-butylperoxycyclohexane and 2, 2-di (tert-butylperoxy) butane; alkyl peresters such as t-butyl peroxypivalate, t-butyl peroxy2-ethylhexanoate, t-butyl peroxyisobutyrate, di-t-butylperoxyhexahydroterephthalate, di-t-butylperoxyazelate, t-butyl peroxy3, 5-trimethylhexanoate, t-butylperoxyacetate, t-butylperoxybenzoate and di-t-butylperoxytrimethyladipate, percarbonates such as diisopropyl peroxydicarbonate, di-sec-butyl peroxydicarbonate and t-butylperoxyisopropyl carbonate, and 2,2' -azobisisobutyronitrile may be used.

These polymerization initiators may be used alone or in combination of 2 or more.

These polymerization initiators can be appropriately selected and used according to the kind and ratio of the addition polymerizable compound having 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 still more preferably 1 to 60% by mass, based on the total mass of the addition polymerizable compound having an ionic group contained in the composition.

When the polymerization treatment is carried out, for example, the composition may be left to stand or stirred at a temperature described later for a predetermined time.

Photopolymerization treatment

In order to initiate photopolymerization, a composition containing an addition polymerizable compound having an ionic group and a 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 irradiated light is not particularly limited, and may be, for example, 0.5W/m ² Above 500W/m ² The following.

The light to be irradiated is not particularly limited as long as it can generate radicals or ions from the photopolymerization initiator. Examples thereof include visible light, ultraviolet light, and near infrared light. Examples of the lamp for generating these rays include a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, a xenon lamp, an ultraviolet LED, a blue LED, a white LED, an H lamp, a D lamp, a V lamp, a carbon arc, a tungsten lamp, a fluorescent lamp, a helium cadmium laser, an argon laser, an Nd: YAG laser, carbon dioxide laser, titanium sapphire laser, excimer laser, and the like. Sunlight may also be used.

The irradiation time and irradiation intensity can be appropriately set depending on 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 any temperature at which polymerization proceeds sufficiently, and is, for example, preferably 5 ℃ to 150 ℃, more preferably 10 ℃ to 100 ℃, and still more preferably 15 ℃ to 80 ℃.

The time required for the photopolymerization treatment may be a time sufficient for the polymerization, and is, for example, 10 seconds to 1 week, preferably 30 seconds to 1 day, and more preferably 1 minute to 1 hour.

The atmosphere in the photopolymerization treatment is not particularly limited, but it is preferable to replace the photopolymerization initiator with an inert gas such as nitrogen or argon in view of improving the 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 perform the thermal polymerization reaction, it is preferable that the composition containing the addition polymerizable compound having an ionic group and the thermal polymerization initiator is heated at an appropriate temperature capable of generating radicals or ions by the thermal polymerization initiator.

The temperature in the polymerization treatment may be any temperature at which polymerization proceeds sufficiently, and is preferably 5 ℃ to 200 ℃ inclusive, more preferably 10 ℃ to 150 ℃ inclusive, and still more preferably 15 ℃ to 100 ℃ inclusive, for example.

The time required for the polymerization treatment may be any time as long as the polymerization is sufficiently carried out, and examples thereof include 1 minute to 1 week, preferably 10 minutes to 5 days, and more preferably 30 minutes to 3 days.

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

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

In the present embodiment, the component (2) and the component (3) may be mixed in any step included in the method for producing the component (1). For example, the following production method (a 5) or the following production method (a 6) may be used.

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

Production method (a 6): comprises a step of adding a compound containing a component B and a component X, a compound containing a component A or a component A and a component X, and a component (2) to a high-temperature component (3) to dissolve the components to obtain a solution h; and a step of cooling the obtained solution h.

In the present embodiment, in the case of producing a composition containing a polymer of an addition polymerizable compound having an ionic group, the following production method (a 7) or the following production method (a 8) can be employed.

Production method (a 7): comprises a step of dissolving a compound containing a component B and a component X, a compound containing a component A or a component A and a component X, and a component (2') in a component (3) to obtain a solution g; and a step of mixing the obtained solution g with a solvent y having a solubility of the perovskite compound in the solvent lower than that of the component (3) used in the step of obtaining a solution; and a step of subjecting a mixture of the component (1), the component (2'), and the component (3) to a polymerization treatment.

Production method (a 8): comprises a step of adding a compound containing a component B and a component X, a compound containing a component A or a component A and a component X, and a component (2') to a high-temperature component (3) to dissolve the components to obtain a solution h; and a step of cooling the obtained solution h; and a step of polymerizing the cooled solution h containing the component (1), the component (2'), and the component (3).

The conditions of the respective steps included in these production methods are the same as those described in embodiment 1 and embodiment 2 of the above-described perovskite compound production method.

[ Process for producing a composition containing component (1), (2), (3) and (5) ]

For example, the same method as the method for producing a composition containing the component (1), the component (2), the component (3) and the component (5) can be employed except that the component (5) is mixed in any of the steps contained in the above-mentioned production methods (a 1) to (a 4).

In the present embodiment, from the viewpoint of improving the dispersibility of the component (1), the component (5) is preferably mixed in any step included in the production method of the perovskite compound having a, B, and X as constituent components of the component (1). For example, the production is preferably performed by the following production method (b 1), production method (b 2), production method (b 3), or production method (b 4).

Production method (b 1): comprises a step of dissolving a compound containing a component B and a component X, a compound containing a component A or a component A and a component X, and a component (2) and a component (5) in a component (3) to obtain a solution g; and a step of mixing the obtained solution g with a solvent y having a solubility of the perovskite compound in the solvent lower than that of the component (3) used in the step of obtaining a solution.

Production method (b 2): comprises a step of adding a compound containing a component B and a component X, a compound containing a component A or a component A and a component X, a component (2) and a component (5) to a high-temperature component (3) to dissolve the components to obtain a solution h; and a step of cooling the obtained solution h.

Production method (b 3): comprises a step of dissolving a compound containing a component B and a component X, a compound containing a component A or a component A and a component X, a component (2') and a component (5) in a component (3) to obtain a solution g; and a step of mixing the obtained solution g with a solvent y in which the solubility of the perovskite compound in the solvent is lower than that of the component (3) used in the step of obtaining a solution; and a step of polymerizing a mixture of the component (1), the component (2'), the component (3) and the component (5).

Production method (b 4): comprises a step of adding a compound containing a component B and a component X, a compound containing a component A or a component A and a component X, a component (2') and a component (5) to a high-temperature component (3) to dissolve the components to obtain a solution h; and a step of cooling the obtained solution h; and a step of subjecting the cooled solution h containing the component (1), the component (2'), the component (3) and the component (5) to a polymerization treatment.

[ Process for producing a composition containing component (1), (2) and (4) ]

The method for producing a composition containing the component (1), the component (2) and the component (4) includes a method of mixing the component (1), the component (2) and the component (4).

The step of mixing the component (1), the component (2) and the component (4) is preferably performed while stirring, from the viewpoint of improving the dispersibility of the component (1).

In the step of mixing the component (1), the component (2), and the component (4), the temperature is not particularly limited, and from the viewpoint of uniform mixing, the temperature is preferably in the range of 0 ℃ to 100 ℃, and more preferably in the range of 10 ℃ to 80 ℃.

Examples of the method for producing the composition containing the component (1), the component (2) and the component (4) include the following production methods (c 1), (c 2) and (c 3).

Production method (c 1): comprises a step of dispersing the component (1) in the component (4) to obtain a dispersion; and (3) mixing the obtained dispersion with the component (2).

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

Production method (c 3): comprises a step of dispersing a mixture of the component (1) and the component (2) in the component (4).

Among the production methods (c 1) to (c 3), the production method (c 1) 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 the component (1) is dispersed in the component (4) and the component (2) by the above-mentioned method.

In the step of obtaining each dispersion included in the production methods of (c 1) to (c 3), the component (4) may be added dropwise to either or both of the components (1) and (2), or either or both of the components (1) and (2) may be added dropwise to the component (4).

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

In each mixing step included in the production methods of (c 1) to (c 3), the component (1) or (2) may be added dropwise to the dispersion, or the dispersion may be added dropwise to the component (1) or (2).

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

When a polymer is used as the component (4), 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 is a solvent capable of dissolving the polymer (resin), and a solvent in which the component (1) used in the present invention is hardly dissolved is preferable.

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

The method for producing the composition containing the component (1), the component (2) and the component (4) may be the following production method (c 4) or production method (c 5).

Production method (c 4): comprises a step of dispersing the component (1) in the component (3) to obtain a dispersion liquid; a step of mixing the obtained dispersion liquid with the component (4) to obtain a mixed liquid; and a step of mixing the obtained mixed solution with the component (2).

The production method (c 5): comprises 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 obtaining a mixed solution containing a polymer of an addition polymerizable compound having an ionic group by performing polymerization treatment on the mixed solution; and a step of mixing the component (4) with a mixed liquid containing a polymer.

[ Process for producing a composition comprising component (1), component (2), component (4) and component (5) ]

The method for producing the composition containing the component (1), the component (2), the component (4) and the component (5) may be the same as the method for producing the composition containing the component (1), the component (2) and the component (4) described above, except that the component (5) is added.

(5) The component (c) may be added in any step included in the production method of the perovskite compound in which a, B and X of the component (1) are constituent components, or may be added in any step included in the production method of the composition containing the component (1), the component (2) and the component (4).

From the viewpoint of improving the dispersibility of the component (1), the component (5) is preferably added in any step included in the production method of the perovskite compound having a, B, and X as constituent components of the component (1).

In the method for producing a composition containing the component (1), the component (2), the component (4) and the component (5), the component (3) solvent can be used, and thus, for example, a dispersion in which the component (1) at least partially coated with the component (5) is dispersed in the component (3), a dispersion in which the component (2) is dispersed in the component (3), or a mixture of the component (4), or a dispersion in which the component (1) and the component (2) at least partially coated with the component (5) are dispersed in the component (3), or a mixture of the component (4) can be obtained to obtain the composition of the present embodiment.

[ method for producing a composition containing component (1), (2) and (4 '), wherein the total content of component (1), (2) and (4') is 90% by mass or more based on the total mass of the composition ]

The method for producing a composition containing the component (1), the component (2) and the component (4 '), wherein the total content of the component (1), the component (2) and the component (4') is 90% by mass or more based on the total mass of the composition includes, for example, the following production method (Y).

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

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

Examples of the above-mentioned production method include the following production methods (d 1) to (d 6).

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

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

Production method (d 3): comprises a step of dispersing the component (2) in a polymerizable compound to obtain a dispersion; and a step of mixing the obtained dispersion with the component (1); and a step of polymerizing the polymerizable compound.

Production method (d 4): comprises a step of dispersing the component (2) in a polymer dissolved in a solvent to obtain a dispersion; and a step of mixing the obtained dispersion with the component (1); and a step of removing the solvent.

Production method (d 5): comprises a step of dispersing a mixture of the component (1) and the component (2) in a polymerizable compound and a step of polymerizing the polymerizable compound.

Production method (d 6): comprises a step of dispersing a mixture of the component (1) and the component (2) in a polymer dissolved in a solvent, and a step of removing the solvent.

The step of removing the solvent in the above-mentioned production method may be a step of allowing the mixture to stand at room temperature to be naturally dried, or 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 ℃ to 300 ℃ for 1 minute to 7 days.

The step of polymerizing the polymerizable compound included in the above-mentioned production method can be carried out by appropriately using a known polymerization reaction such as radical polymerization.

For example, in the case of radical polymerization, a radical polymerization initiator is added to a mixture of the component (1), the component (2) and a polymerizable compound to generate radicals, thereby allowing a polymerization reaction to proceed.

The radical polymerization initiator is not particularly limited, and examples thereof include a photo radical polymerization initiator.

Examples of the photo radical polymerization initiator include bis (2, 4, 6-trimethylbenzoyl) -phenylphosphine oxide and the like.

[ Process for producing a composition containing component (1), component (2), component (4 ') and component (5) in a total content ratio of 90% by mass or more of the total of component (1), component (2), component (4') and component (5) ]

The method for producing a composition containing the components (1), (2), (4 ') and (5) in a total content ratio of 90% by mass or more of the components (1), (2), (4') and (5) with respect to the total mass of the composition may be the same as the method for producing a composition containing the components (1), (2) and (4 ') in a total content ratio of 90% by mass or more of the components (1), (2) and (4') with respect to the total mass of the composition, except that the component (5) is added in any step included in the method for producing a composition containing the components (1), (2) and (4 ') in a total content ratio of 90% by mass or more of the components (1), (2) and (4') with respect to the total mass of the composition.

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 having a, B, and X as constituent components (1).

Any step included in the above-described method for producing a perovskite compound.

A step of mixing the polymerizable compounds (1) and (2).

A step of mixing the polymers (1) and (2) with a solvent.

[ method for producing composition containing component (6) ]

The method for producing the composition containing the component (6) may be the same as the method for producing the composition, except that the component (6) is further mixed. Before mixing the component (1) and the component (2), the component (1) and the component (6) are preferably mixed, and for example, the following production method (a 1-1) or the following production method (a 2-1) can be used.

Production method (a 1-1): comprises a step of mixing the components (1) and (3), a step of mixing the mixture of the components (1) and (3) with the component (6), and a step of mixing the component (2) with a mixture containing the components (1), (3) and (6).

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

[ mixing Process with component (1) -1 ]

The method for producing the composition of the present embodiment may further include a step of mixing the components (1) -1. This step can be carried out by preparing a dispersion liquid containing a perovskite compound having an emission peak wavelength different from that of the component (1) and a solvent, and mixing the dispersion liquid with a mixed liquid containing the component (1) and the component (2) as essential components and other optional components. In this step, as the component (1) -1, a mixed solution containing the component (1) -1, the component (2) as an arbitrary component, and the other arbitrary components can be used. The mixed solution containing the component (1) -1 and the component (2) as an optional component and the above-mentioned other optional components can be produced by the same method as the mixed solution containing other optional components, except that the components (1) and (2) described above are essential components.

Determination of perovskite Compound

The amount of the perovskite compound contained in the composition of the present invention is measured using inductively coupled plasma mass spectrometry ICP-MS (for example, perkinElmer, elandcii) and ion chromatography (for example, thermofischer scientific, integorion).

The perovskite compound is dissolved in a good solvent such as N, N-dimethylformamide and the like, and then measured.

Measurement of luminescence Spectrum

The emission spectrum of the composition of the present invention was measured at room temperature under an atmospheric pressure with an excitation light of 450nm using an absolute PL quantum yield measuring apparatus (for example, C9920-02, manufactured by Hamamatsu photonics corporation).

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

The composition containing the component (1), the component (2) and the component (4) was mixed so that the concentration of the perovskite compound contained in the composition became 2000ppm (. Mu.g/g), and the emission spectrum was measured. The same applies to the case where component (4) is replaced with component (4').

Evaluation of luminescence Peak when 2 perovskite Compounds were mixed 1

A perovskite compound (perovskite compound 2) having a wavelength of emission peak different from that of the perovskite compound is mixed in 1mL of the dispersion composition of the present invention containing the perovskite compound (perovskite compound 1). The emission spectra were measured before and after mixing of 2 kinds of perovskite compounds, and as evaluation indices of the emission spectra, the absolute values of (the emission peak wavelength (nm) of the perovskite compound 1 before mixing) - (the emission peak wavelength (nm) of the perovskite compound 1 after mixing), and the absolute values 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 were calculated.

Evaluation of luminescence Peak when 2 perovskite Compounds were mixed 2

The composition of the present invention containing a perovskite compound (perovskite compound 1) is mixed with a perovskite compound (perovskite compound 2) having a different emission peak wavelength from that of the perovskite compound, and the resulting mixture is formed into a film and then cut into a thickness of 100 μm and 1cm × 1cm. The emission spectra were measured before and after mixing of 2 kinds of perovskite compounds, and as evaluation indices of the emission spectra, the absolute values of (the emission peak wavelength (nm) of the perovskite compound 1 before mixing)) - (the emission peak wavelength (nm) of the perovskite compound 1 after mixing), and the absolute values 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 were calculated.

In the composition of the embodiment, the evaluation of the emission peak in the case of mixing 2 perovskite compounds measured by the above-described measurement method may be 23nm or less, 20nm or less, 15nm or less, and the number of peaks may be 2.

In one aspect of the present invention, the evaluation of the emission peak of the mixed 2 perovskite compounds measured by the above-described measurement method is preferably 0nm to 23nm, more preferably 0nm to 20nm, and still more preferably 0nm to 15nm.

The emission peak of the mixture of 2 perovskite compounds measured by the above-mentioned measurement method is not particularly limited, and for example, the absolute value of the difference in wavelength is preferably 30nm or more, more preferably 50nm or more, and further preferably 100nm or more for the 2 emission peak wavelengths observed. The minimum emission intensity in the wavelength region between the 2 emission peaks is preferably 80% or less, more preferably 50% or less, and still more preferably 30% or less of the emission intensity of the higher emission peak among the 2 emission peak wavelengths.

< film >

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

The shape of the film is not particularly limited, and may be any shape such as a sheet or a rod. In the present specification, the term "rod-like shape" refers to, for example, a shape having anisotropy. As the shape having anisotropy, a plate shape having different lengths of each side is exemplified.

The thickness of the film may be 0.01 μm or more and 1000mm or less, 0.1 μm or more and 10mm or less, or 1 μm or more and 1mm or less.

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

The film may be a single layer or a multilayer. In the case of a plurality of layers, the same type of composition may be used for each layer, or different types of compositions may be used for each layer.

The film can be formed on the substrate by, for example, the manufacturing methods (i) to (iV) of the laminated structure described later. The film may be obtained by peeling from the substrate.

< laminated Structure >

The laminate structure of the present invention has a plurality of layers, at least one of which is the above-described thin film.

Among the plurality of layers of the laminated structure, the layers other than the film include any of a substrate, a barrier layer, a light scattering layer, and the like.

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

(substrate)

The layer that the laminated structure of the present invention may have is not particularly limited, and a substrate may be mentioned.

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

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

Fig. 1 is a cross-sectional view schematically showing the structure of the laminated structure of the present embodiment. The 1 st stacked structure 1a is provided with the film 10 of the present embodiment between a1 st substrate 20 and a2 nd substrate 21. The film 10 is sealed by a sealing layer 22.

One aspect of the present invention is a laminated structure 1a including a1 st substrate 20, a2 nd substrate 21, a film 10 of the present embodiment positioned between the 1 st substrate 20 and the 2 nd substrate 21, and a sealant 22, wherein the sealant is disposed on a surface of the film 10 not in contact with the 1 st substrate 20 and the 2 nd substrate 21.

(Barrier layer)

The layer that the laminated structure of the present invention may have is not particularly limited, and a barrier layer may be mentioned. The composition may contain a barrier layer from the viewpoint of protecting the composition from water vapor in the outside air and air in the atmosphere.

The barrier layer is not particularly limited, but a transparent barrier layer is preferable from the viewpoint of extracting emitted light. As the barrier layer, for example, a polymer such as polyethylene terephthalate, a known barrier layer such as a glass film, or the like can be used.

(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. The light scattering layer may be included from the viewpoint of effectively utilizing incident light.

The light scattering layer is not particularly limited, but a transparent layer is preferable 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 a diffusion enhancement film can be used.

< light emitting device >

The light-emitting device of the present invention can be obtained by combining the composition or the layered structure of the embodiment of the present invention with a light source. The light-emitting device is a device that emits light by irradiating a composition or a layered structure provided at a subsequent stage with light emitted from a light source, thereby emitting the composition or the layered structure and extracting the light. Among the plurality of layers of the laminated structure in the light-emitting device, the film, the substrate, the barrier layer, and the layer other than the light scattering layer may be any of a light reflecting member, a brightness enhancing member, a prism sheet, a light guide plate, and an inter-element dielectric material layer.

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

(light source)

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

(light reflecting Member)

The layer that the laminated structure constituting the light-emitting device of the present invention may have is not particularly limited, and a light-reflecting member may be mentioned. The light-reflecting member may be contained from the viewpoint of irradiating the composition or the layered structure with light from a light source. The light reflecting member is not particularly limited, but may be a reflective film.

As the reflective film, for example, a known reflective film such as a mirror, a reflective particle film, a reflective metal film, or a reflector can be used.

(Brightness enhancement section)

The layer that the laminated structure constituting the light-emitting device of the present invention may have is not particularly limited, and a luminance enhancing portion may be mentioned. The luminance increasing unit may be included from the viewpoint of reflecting and returning a part of the light in the direction in which the light is transmitted.

(prism sheet)

The layer that the laminated structure constituting the light-emitting device of the present invention may have is not particularly limited, and a prism sheet may be mentioned. The prism sheet typically has a base material portion and a prism portion. The base material portion may be omitted depending on the adjacent members. The prism sheet may be bonded to an adjacent member via any suitable adhesive layer (e.g., an adhesive layer). The prism sheet is configured by arranging a plurality of unit prisms projecting toward the side opposite to the viewing side (back side). By disposing the convex portion of the prism sheet toward the rear surface side, light transmitted through the prism sheet is easily condensed. Further, if the convex portion of the prism sheet is disposed toward the rear surface side, the light that is not incident on the prism sheet and is reflected is less, and a display with high luminance can be obtained, as compared with the case where the convex portion is disposed toward the viewing side.

(light guide plate)

The layer that the laminated structure constituting the light-emitting device of the present invention may have is not particularly limited, and a light guide plate may be mentioned. As the light guide plate, any appropriate light guide plate can be used, for example, a light guide plate having a lens pattern formed on the back surface side, a light guide plate having a prism shape or the like formed on the back surface side and/or the viewing side, and the like, so that light from the lateral direction can be deflected in the thickness direction.

(dielectric material layer between elements)

The layer that the laminated structure constituting the light-emitting device of the present invention may have is not particularly limited, and a layer (dielectric material layer between elements) composed of 1 or more dielectric materials on the optical path between adjacent elements (layers) may be mentioned.

The medium contained in the dielectric material layer between elements is not particularly limited, and includes vacuum, air, gas, optical material, adhesive, optical adhesive, glass, polymer, solid, liquid, gel, cured material, optical bonding material, refractive index matching or non-matching material, graded index material, cladding or anti-cladding material, spacer, silica gel, brightness enhancement material, scattering or diffusing material, reflective or anti-reflective material, wavelength selective anti-reflective material, color filter, or suitable medium known in the art.

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

Specifically, there may be mentioned (E1) a backlight (edge type backlight) in which the composition of the present invention is sealed in a glass tube or the like, and the sealed composition is disposed between a blue light emitting diode as a light source and a light guide plate so as to extend along an end face (side face) of the light guide plate, and blue light is converted into green light or red light.

Further, (E2) a backlight (surface mount type backlight) in which the composition of the present invention is formed into a sheet, a film sealed by sandwiching the sheet with 2 barrier films is provided on a light guide plate, and blue light emitted from a blue light emitting diode provided on an end face (side face) of the light guide plate onto the sheet through the light guide plate is converted into green light or red light is also exemplified.

Further, there may be mentioned (E3) a backlight (on-chip backlight) in which the composition of the present invention is dispersed in a resin or the like, and the composition is disposed in the vicinity of a light emitting portion of a blue light emitting diode to convert irradiated blue light into green light or red light.

Further, (E4) a backlight in which the composition of the present invention is dispersed in a resist, and the resultant is provided on a color filter to convert blue light irradiated from a light source into green light or red light.

In addition, a specific example of the light emitting device according to the present invention is an illumination device which is formed by molding the composition according to the embodiment of the present invention, is disposed at a stage subsequent to a blue light emitting diode as a light source, converts blue light into green light or red light, and emits white light.

< display >

As shown in fig. 2, the display 3 of the present embodiment includes a liquid crystal panel 40 and the light emitting device 2 in this order from the viewing side. A light-emitting device (2) is provided with a2 nd laminated structure (1 b) and a light source (30). The 2 nd laminated structure 1b is a laminated structure of the 1 st laminated structure 1a, further including a prism sheet 50 and a light guide plate 60. The display may also be provided with any suitable other components.

One side 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 1 st stacked structure 1a, and a light source 30 are stacked in this order.

(liquid crystal panel)

The liquid crystal panel typically includes a liquid crystal cell, a viewing-side polarizing plate disposed on a viewing side of the liquid crystal cell, and a back-side polarizing plate disposed on a back side of the liquid crystal cell. The viewing-side polarizing plate and the back-side polarizing plate may be arranged such that their absorption axes are substantially orthogonal or parallel to each other.

(liquid Crystal cell)

The liquid crystal cell has a pair of substrates and a liquid crystal layer as a display medium sandwiched between the substrates. In a general configuration, a color filter and a black matrix are provided on one substrate, and a switching element for controlling an electro-optical characteristic of a liquid crystal, a scanning line for supplying a gate signal to the switching element, a signal line for supplying a source signal to the switching element, a pixel electrode, and a counter electrode are provided on the other substrate. The spacing (cell gap) between the substrates can be controlled by spacers or the like. An alignment film made of polyimide, for example, may be provided on the substrate on the side in contact with the liquid crystal layer.

(polarizing plate)

The polarizing plate typically has a polarizer and protective layers disposed on both sides of the polarizer. The polarizing plate is typically an absorption type polarizing plate.

As the polarizing plate, any suitable polarizing plate may be used. Examples thereof include a film obtained by uniaxially stretching 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, by adsorbing a dichroic substance such as iodine or a dichroic dye, and a polyolefin-based oriented film such as a dehydrated polyvinyl alcohol or a desalted polyvinyl chloride. Among them, a polarizing plate obtained by adsorbing a dichroic material such as iodine on a polyvinyl alcohol film and uniaxially stretching the film has a high polarization dichroism ratio, and is therefore particularly preferable.

Examples of applications of the composition of the present invention include a wavelength conversion material for a Light Emitting Diode (LED).

<LED>

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

Examples of the LED containing the composition of the present invention include the following: the composition of the present invention and conductive particles such as ZnS are mixed and laminated in a film form, an n-type transport layer is laminated on one surface, and a p-type transport layer is laminated on the other surface, and when a current is applied, holes of the p-type semiconductor and electrons of the n-type semiconductor cancel charges in the particles of the component (1) and the component (2) contained in the composition at the junction surface, and light is emitted.

< solar cell >

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

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

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

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

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

< method for producing laminated Structure >

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

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

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

Production method (iii): comprises a step of bonding a composition containing the component (1), the component (2) and the component (4 '), that is, a composition in which the total content of the component (1), the component (2) and the component (4') is 90% by mass or more based on the total mass of the composition, to a substrate.

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

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

The step of coating on the substrate included in the production method of (i), (ii), and (iv) is not particularly limited, and known coating and painting methods such as a gravure coating method, a bar coating method, a printing method, a spray coating method, a spin coating method, a dipping method, and a die coating method can be used.

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

The adhesive is not particularly limited as long as it does not dissolve the compounds of component (1) and component (2), and a known adhesive 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 the arbitrary film to be bonded include a reflective film and a diffusion film.

In the step of bonding the film, any adhesive may be used.

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

< method for producing light-emitting device >

For example, a method for manufacturing a light source includes the step of disposing the composition or the laminated structure on an optical path of a subsequent stage from the light source.

The technical scope of the present invention is not limited to the above-described embodiments, and various modifications may be made without departing from the spirit of the present invention.

Examples

The present invention will be described more specifically below with reference to examples and comparative examples, but the present invention is not limited to the following examples.

(measurement of concentration 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-dimethylformamide is added, whereby the perovskite compound is dissolved.

Then, measurement was carried out by using ICP-MS (PerkinElmer, ELAN DRCII) and an ion chromatograph (ThermoFischer scientific, integrion).

(measurement of luminescence Spectrum)

The emission spectra of the compositions obtained in examples 1 to 18 and comparative examples 1 to 3 were measured at room temperature under the atmosphere with an excitation light of 450nm using an absolute PL quantum yield measuring apparatus (C9920-02, manufactured by Hamamatsu photonics Co., ltd.).

(2 evaluation of luminescence peaks when perovskite Compounds are blended)

To 1mL of the dispersion compositions obtained in examples 1 to 18 and comparative examples 1 to 3, different perovskite compounds were added, and the resulting mixture was adjusted to 200ppm (μ g/g) each using n-hexane. The emission spectra were measured before and after mixing of 2 perovskite compounds, and the absolute value of (the emission peak (nm) of the perovskite compound 1 before mixing)) - (the emission peak (nm) of the perovskite compound 1 after mixing), and the absolute value of (the emission peak (nm) of the perovskite compound 2 before mixing)) - (the emission peak (nm) of the perovskite compound 2 after mixing), and the number of peaks were calculated as evaluation indices of the emission spectra.

(observation Using scanning Electron microscope)

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

In the compositions in which agglomerates were observed, the average Ferrett diameter was the average of the Ferrett diameters of 20 agglomerates.

Observation of perovskite Compound with Transmission Electron microscope

The perovskite compound was observed using a transmission electron microscope (JEM-2200 FS, manufactured by nippon electronics co., ltd.). For the sample for observation, the perovskite compound was extracted from the dispersion composition containing the perovskite compound to the grid with the supporting film, and then the acceleration voltage was set to 200kV for observation.

The average Ferrett diameter is the average of the Ferrett diameters of 20 perovskite compounds.

(Synthesis of composition)

[ example 1]

0.814g cesium carbonate, 40mL 1-octadecene solvent, and 2.5mL oleic acid were combined. Cesium carbonate solution 1 was prepared by heating at 150 ℃ for 1 hour while stirring with a magnetic stirrer under nitrogen gas.

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

After the lead bromide dispersion was warmed to a temperature of 160 ℃, 1.6mL of the above cesium carbonate solution 1 was added. After the addition, the reaction vessel was immersed in ice water and cooled to room temperature to obtain a dispersion.

Subsequently, the dispersion was centrifuged at 10000rpm for 5 minutes, and the precipitate was separated to obtain a precipitate perovskite compound 1. After dispersing the perovskite compound 1 in 5mL of n-hexane, 100 μ L of the dispersion was taken out and dispersed in 0.9mL of n-hexane, thereby obtaining a dispersion 1 containing the perovskite compound 1 and a solvent.

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

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

When the X-ray diffraction pattern of the compound recovered by naturally drying the solvent was measured by an X-ray diffraction measurement apparatus (XRD, cuK α ray, X' pertiprmpd, manufactured by seiko corporation), a peak derived from (hkl) = (001) was present at a position of 2 θ =14 °, and it was confirmed that the compound had a three-dimensional perovskite crystal structure.

The perovskite compound observed by TEM had an average Ferrett diameter of 11nm.

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

After the lead bromide-lead iodide dispersion liquid was warmed to a temperature of 160 ℃, 1.6mL of the above cesium carbonate solution 1 was added. After the addition, the reaction vessel was immersed in ice water and cooled to room temperature to obtain a dispersion.

Subsequently, the dispersion was centrifuged at 10000rpm for 5 minutes, and the precipitate was separated to obtain a precipitate perovskite compound 2. After dispersing the perovskite compound 2 in 5mL of n-hexane, 100 μ L of the dispersion was taken out and dispersed in 0.9mL of n-hexane, thereby obtaining a dispersion 2 containing the perovskite compound 2 and a solvent.

The perovskite compound observed with TEM had an average feret diameter of 19nm.

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

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

After 3. Mu.L of 4-vinylbenzylamine was mixed with dispersion 1 containing perovskite compound 1 and a solvent, 30mg of 2,2' -azobisisobutyronitrile was mixed. After replacement with nitrogen, the mixture was polymerized at 60 ℃ for 4 hours with stirring by a stirrer to obtain a composition. In the composition, the mass ratio is perovskite compound 1/4-vinylbenzylamine =0.045.

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

Further, 0.1mL and 0.1mL of the dispersion 2 containing the perovskite compound 2 and the solvent were mixed with 0.8mL of n-hexane. The emission spectrum after mixing was measured by a quantum yield measuring apparatus. As a result, the peak of 530nm, which is the emission peak wavelength of the perovskite compound 1, and the peak of 622nm, which is the emission peak wavelength of the perovskite compound 2, were maintained.

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

[ example 2]

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

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

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

As shown in fig. 3, when the dispersion liquid 2 was mixed in the composition of example 2, the peak of 520nm, which is the emission peak wavelength of the perovskite compound 1, and the peak of 645nm, which is the emission peak wavelength of the perovskite compound 2, were maintained.

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

[ example 3]

10mg of 4-carboxystyrene was mixed in the dispersion liquid 1 containing the perovskite compound 1 and the solvent described in example 1, and 30mg of 2,2' -azobisisobutyronitrile was then mixed. After the replacement with nitrogen, the mixture was polymerized while stirring with a stirrer at 60 ℃ for 1 hour to obtain a composition. In the composition, the mass ratio is [ perovskite compound 1]/[ 4-carboxystyrene ] =0.013.

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

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

[ example 4]

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

After the perovskite compound 1 was diluted with n-hexane to 200ppm (μ g/g), the peak of the luminescence spectrum measured by a quantum yield measuring apparatus was 522nm.

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

As shown in fig. 3, when the dispersion liquid 2 was mixed in the composition of example 4, the peak at 516nm, which is the emission peak wavelength of the perovskite compound 1, and the peak at 642nm, which is the emission peak wavelength of the perovskite compound 2, were maintained.

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

[ example 5]

10mg of 2-acrylamido-2-methylpropanesulfonic acid was mixed with dispersion 1 containing perovskite compound 1 and a solvent described in example 1, and 30mg of 2,2' -azobisisobutyronitrile was then mixed therewith. After the replacement with nitrogen, the mixture was polymerized while stirring with a stirrer at 60 ℃ for 1 hour to obtain a composition. In the composition, the mass ratio is [ perovskite compound 1]/[ 2-acrylamide-2-methylpropanesulfonic acid ] =0.013.

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

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

[ example 6]

10mg of 3- [ [2- (methacryloyloxy) ethyl ] dimethylammonium ] propionate was mixed with the dispersion 1 containing the perovskite compound 1 described in example 1 and the solvent, and then 30mg of 2,2' -azobisisobutyronitrile was mixed. After the replacement with nitrogen, the mixture was polymerized while stirring with a stirrer at 60 ℃ for 1 hour to obtain a composition. In the composition, the mass ratio is [ perovskite compound 1]/[3- [ [2- (methacryloyloxy) ethyl ] dimethylammonium ] propionate ] =0.013.

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

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

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

[ example 7]

A composition was obtained in the same manner as in example 6 above, except that 20mg of 3- [ [2- (methacryloyloxy) ethyl ] dimethylammonium ] propionate was used and the mass ratio [ perovskite compound 1]/[3- [ [2- (methacryloyloxy) ethyl ] dimethylammonium ] propionate ] = 0.0065.

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

As shown in FIG. 3, when the dispersion liquid 2 was mixed with the composition of example 7, the peak value at 531nm, which is the emission peak wavelength of the perovskite compound 1, and the peak value at 617nm, which is the emission peak wavelength of the perovskite compound 2, were maintained.

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

[ example 8]

After 3. Mu.L of methacrylic acid was mixed with the dispersion 1 containing the perovskite compound 1 and the solvent described in example 1, 30mg of 2,2' -azobisisobutyronitrile was mixed. After the replacement with nitrogen, the mixture was polymerized while stirring with a stirrer at 60 ℃ for 1 hour to obtain a composition. In the composition, the mass ratio is [ perovskite compound 1]/[ methacrylic acid ] =0.043.

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

0.1mL of the above composition and 0.1mL of dispersion 2 containing perovskite compound 2 and a solvent were mixed with 0.8mL of n-hexane. The emission spectrum after mixing was measured by a quantum yield measuring apparatus. As a result, the peak of the perovskite compound 1, i.e., 531nm, and the peak of the perovskite compound 2, i.e., 633nm, were maintained.

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

[ example 9]

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

0.1mL of the above composition and 0.1mL of dispersion 2 containing perovskite compound 2 and a solvent were mixed with 0.8mL of n-hexane. The emission spectrum after mixing was measured by a quantum yield measuring apparatus. The results are shown in FIG. 4.

As shown in fig. 4, when the dispersion liquid 2 was mixed in the composition of example 9, the peak of 522nm, which is the emission peak wavelength of the perovskite compound 1, and the peak of 636nm, which is the emission peak wavelength of the perovskite compound 2, were maintained.

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

[ example 10]

After 5. Mu.L of methacrylic acid was mixed with the dispersion 2 containing the perovskite compound 2 and the solvent described in example 1, 30mg of 2,2' -azobisisobutyronitrile was mixed. After the replacement with nitrogen, the mixture was polymerized while stirring with a stirrer at 60 ℃ for 1 hour to obtain a composition. In the composition, the mass ratio is [ perovskite compound 2]/[ methacrylic acid ] =0.026.

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

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

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

[ example 11]

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

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

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

[ example 12]

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

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

0.1mL and 0.1mL of the dispersion 1 containing the perovskite compound 1 and the solvent were mixed with 0.8mL of n-hexane. The emission spectrum after mixing was measured by a quantum yield measuring apparatus. The results are shown in FIG. 4.

As shown in fig. 4, when the dispersion liquid 1 was mixed in the composition of example 12, the peak of 626nm, which is the emission peak wavelength of the perovskite compound 2, and the peak of 520nm, which is the emission peak wavelength of the perovskite compound 1, were maintained.

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

[ example 13]

After 10. Mu.L of 4-vinylbenzylamine was mixed with the dispersion 1 containing the perovskite compound 1 and the solvent described in example 1, 30mg of 2,2' -azobisisobutyronitrile was mixed therewith. After the replacement with nitrogen, the mixture was polymerized while stirring with a stirrer at 60 ℃ for 1 hour to obtain a composition. In the composition, the mass ratio is [ perovskite compound 1]/[ 4-vinylbenzylamine ] =0.013.

Subsequently, a methacrylic resin (PMMA, sumitomo. Methacrylic resin, MH, molecular weight of about 12 ten thousand, specific gravity of 1.2 g/ml) was 16.5% by mass by mixing toluene with the methacrylic resin, and then heated at 60 ℃ for 3 hours to obtain a solution in which the polymer was dissolved.

0.15g of a composition comprising a polymer of the perovskite compound 1 and an addition polymerizable compound having an ionic group and a solvent, 0.15g of a dispersion liquid 2 comprising the perovskite compound 2 and a solvent, and 0.913g of a solution in which the polymer is dissolved were mixed, and then the solvent was evaporated by natural drying, thereby obtaining compositions each having a concentration of the perovskite compound of 2000ppm (. Mu.g/g).

The obtained composition was cut into pieces of 1cm × 1cm × 100 μm, and then the emission spectrum was measured by a quantum yield measuring apparatus. The results are shown in FIG. 4.

As shown in fig. 4, the composition of example 13 maintained the peak of 532nm, which is the emission peak wavelength of the perovskite compound 1, and the peak of 624nm, which is the emission peak wavelength of the perovskite compound 2, respectively.

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

[ example 14]

Polysilazane (Durazane 1500SlowCure, manufactured by mercksman materials) was mixed with the dispersion 1 containing the perovskite compound 1 and the solvent described in example 1. In the dispersion, the molar ratio was Si/Pb =76.0. After further mixing 30. Mu.L of methacrylic acid, 30mg of 2,2' -azobisisobutyronitrile was mixed. After the replacement with nitrogen, the mixture was polymerized while stirring with a stirrer at 60 ℃ for 1 hour to obtain a composition. In the composition, the mass ratio is [ perovskite compound 1]/[ methacrylic acid ] =0.0043.

After the perovskite compound 1 was diluted with n-hexane to 200ppm (μ g/g), the peak of the luminescence spectrum measured by a quantum yield measuring apparatus was 518nm.

0.1mL of the above composition and 0.1mL of dispersion 2 containing perovskite compound 2 and a solvent were mixed in 0.8mL of n-hexane. The emission spectrum after mixing was measured by a quantum yield measuring apparatus. The results are shown in FIG. 5.

As shown in fig. 5, when the dispersion liquid 2 was mixed in the composition of example 14, the peak of 517nm, which is the emission peak wavelength of the perovskite compound 1, and the peak of 639nm, which is the emission peak wavelength of the perovskite compound 2, were maintained.

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

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

[ example 15]

Polysilazane (Durazane 1500SlowCure, manufactured by mercksman materials) was mixed with the dispersion 1 containing the perovskite compound 1 and the solvent described in example 1. In the dispersion, the molar ratio was Si/Pb =76.0. After further mixing 20. Mu.L of 4-vinylbenzylamine, 30mg of 2,2' -azobisisobutyronitrile was mixed. After the replacement with nitrogen, the mixture was polymerized while stirring with a stirrer at 60 ℃ for 1 hour to obtain a composition. In the composition, the mass ratio is [ perovskite compound 1]/[ 4-vinylbenzylamine ] =0.0067.

After the perovskite compound 1 was diluted with n-hexane to 200ppm (μ g/g), the peak of the luminescence spectrum measured by a quantum yield measuring apparatus was 520nm.

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

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

[ example 16]

Polysilazane (Durazane 1500SlowCure, manufactured by merck-bashman materials corporation) was mixed with the dispersion liquid 2 containing the perovskite compound 2 and the solvent described in example 1. In the dispersion, the molar ratio was Si/Pb =22.8. After further mixing 5. Mu.L of methacrylic acid, 30mg of 2,2' -azobisisobutyronitrile was mixed. After the replacement with nitrogen, the mixture was polymerized while stirring with a stirrer at 60 ℃ for 1 hour to obtain a composition. In the composition, the mass ratio is [ perovskite compound 2]/[ methacrylic acid ] =0.026.

After the perovskite compound 2 was diluted with n-hexane to 200ppm (μ g/g), the peak of the luminescence spectrum measured by a quantum yield measuring apparatus was 640nm.

0.1mL and 0.1mL of the dispersion 1 containing the perovskite compound 1 and the solvent were mixed with 0.8mL of n-hexane. The emission spectrum after mixing was measured by a quantum yield measuring apparatus. As a result, the peak of the perovskite compound 1 having an emission peak wavelength of 518nm and the peak of the perovskite compound 2 having an emission peak wavelength of 642nm were maintained.

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

[ example 17]

Polysilazane (Durazane 1500SlowCure, manufactured by merck-bashman materials corporation) was mixed with the dispersion liquid 2 containing the perovskite compound 2 and the solvent described in example 1. In the dispersion, the molar ratio was Si/Pb =22.8. After further mixing 10. Mu.L of methacrylic acid, 30mg of 2,2' -azobisisobutyronitrile was mixed. After replacement with nitrogen, the mixture was polymerized at 60 ℃ with stirring for 1 hour by a stirrer to obtain a composition. In the composition, the mass ratio is [ perovskite compound 2]/[ methacrylic acid ] =0.013.

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

0.1mL of the above composition and 0.1mL of dispersion 1 containing perovskite compound 1 and a solvent were mixed in 0.8mL of n-hexane. The emission spectrum after mixing was measured by a quantum yield measuring apparatus. As a result, the peak of the perovskite compound 1 having an emission peak wavelength of 518nm and the peak of the perovskite compound 2 having an emission peak wavelength of 640nm were maintained.

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

[ example 18]

Polysilazane (Durazane 1500SlowCure, manufactured by merck-basmann materials) was mixed into the dispersion liquid 2 containing the perovskite compound 2 and the solvent described in example 1. In the dispersion, the molar ratio was Si/Pb =22.8. After further mixing 30. Mu.L of methacrylic acid, 30mg2,2' -azobisisobutyronitrile was mixed. After the replacement with nitrogen, the mixture was polymerized while stirring with a stirrer at 60 ℃ for 1 hour to obtain a composition. In the composition, the mass ratio is [ perovskite compound 2]/[ methacrylic acid ] =0.0043.

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

0.1mL of the above composition and 10.1mL of a dispersion containing the perovskite compound 1 and the solvent were mixed with 0.8mL of n-hexane. The emission spectrum after mixing was measured by a quantum yield measuring apparatus. The results are shown in FIG. 5.

As shown in FIG. 5, when dispersion 1 was mixed with the composition of example 18, the peak of 521nm, which is the emission peak wavelength of perovskite compound 1, and the peak of 647nm, which is the emission peak wavelength of perovskite compound 2, were maintained.

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

The average Ferrett diameter of the agglomerates contained in the composition was 0.3. Mu.m.

Comparative example 1

0.1mL of the dispersion 1 containing the perovskite compound 1 and the solvent described in example 1 and 0.1mL of the dispersion 2 containing the perovskite compound 2 and the solvent were mixed with 0.8mL of n-hexane. The emission spectrum after mixing was measured by a quantum yield measuring apparatus. The results are shown in FIG. 6.

As shown in fig. 6, in comparative example 1, a new emission peak wavelength at 559nm, which is different from the emission peak wavelength of the perovskite compound 1 and the emission peak wavelength of the perovskite compound 2, was emitted.

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

Comparative example 2

After 10. Mu.L of styrene was mixed in the dispersion 1 containing the perovskite compound 1 and the solvent described in example 1, 30mg of 2,2' -azobisisobutyronitrile was mixed. After the replacement with nitrogen, the mixture was polymerized while stirring with a stirrer at 60 ℃ for 1 hour to obtain a composition. In the composition, the mass ratio is [ perovskite compound 1]/[ styrene ] =0.014.

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

As shown in fig. 6, in comparative example 2, a new emission peak wavelength at 571nm, which is different from the emission peak wavelength of the perovskite compound 1 and the emission peak wavelength of the perovskite compound 2, was emitted.

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

Comparative example 3

After 10. Mu.L of methyl methacrylate was mixed with the dispersion 1 containing the perovskite compound 1 and the solvent described in example 1, 30mg of 2,2' -azobisisobutyronitrile was mixed. After the replacement with nitrogen, the mixture was polymerized while stirring with a stirrer at 60 ℃ for 1 hour to obtain a composition. In the composition, the mass ratio [ perovskite compound 1]/[ methyl methacrylate ] =0.014.

As shown in fig. 6, in comparative example 3, a new emission peak wavelength of 545nm was emitted, which was different from the emission peak wavelength of the perovskite compound 1 and the emission peak wavelength of the perovskite compound 2.

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

The compositions of examples 1 to 18 and comparative examples 1 to 3, and the results of evaluation 1 and 2 of emission peaks when 2 perovskite compounds were mixed are shown in table 1 below. In table 1, "(1) component/(2) component (mass ratio)" represents a mass ratio obtained by dividing the mass of the perovskite compound ((1) component) contained in the composition by the mass of the addition polymerizable compound having an ionic group or the polymer thereof ((2) component).

TABLE 1

From the above results, it is understood that the compositions of examples 1 to 18 of the present invention, in which 2 kinds of perovskite compounds are mixed, can maintain the unique emission wavelengths of the respective perovskite compounds even when 2 kinds of perovskite compounds having different emission wavelengths are mixed. In contrast, in comparative examples 1 to 3, emission peaks of new wavelengths different from the intrinsic emission wavelengths of the respective perovskite compounds were emitted.

[ reference example 1]

The compositions described in examples 1 to 18 were sealed in a glass tube or the like after removing the solvent as necessary, and then placed between a blue light emitting diode as a light source and a light guide plate, thereby producing a backlight capable of converting blue light of the blue light emitting diode into green light or red light.

[ reference example 2]

The compositions described in examples 1 to 18 were subjected to sheet formation after removing the solvent as needed to obtain resin compositions, and the resin compositions were sandwiched and sealed by 2 barrier films and placed on a light guide plate to produce a backlight capable of converting blue light, which was irradiated from a blue light emitting diode placed on an end face (side face) of the light guide plate to the sheet through the light guide plate, into green light or red light.

[ reference example 3]

The compositions described in examples 1 to 18 were, if necessary, subjected to solvent removal, and then placed in the vicinity of the light-emitting portion of a blue light-emitting diode, thereby producing a backlight capable of converting irradiated blue light into green light or red light.

[ reference example 4]

The wavelength converting materials can be obtained by removing the solvent from the compositions described in examples 1 to 18, if necessary, mixing the resist, and then removing the solvent. By disposing the obtained wavelength conversion material between the blue light emitting diode as a light source and the light guide plate or at the rear stage of the OLED as a light source, a backlight capable of converting blue light of the light source into green light or red light is manufactured.

[ reference example 5]

An LED was obtained by mixing the compositions described in examples 1 to 18 with conductive particles such as ZnS to form a film, and laminating an n-type transport layer on one surface and a p-type transport layer on the other surface. When a current is applied, the holes of the p-type semiconductor and the electrons of the n-type semiconductor cancel electric charges in the perovskite compound on the junction surface, and light can be emitted.

[ reference example 6]

A dense layer of titanium oxide was laminated on the surface of a fluorine-doped tin oxide (FTO) substrate, a porous alumina layer was laminated thereon, the compositions described in examples 1 to 18 were laminated thereon, the solvent was removed, a hole transport layer such as 2,2', 7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9,9' -spirobifluorene (Spiro-OMeTAD) was laminated thereon, and a silver (Ag) layer was laminated thereon to fabricate a solar cell.

[ reference example 7]

The resin composition containing the composition of the present invention can be obtained by mixing the composition described in examples 1 to 18 with a resin and then molding the mixture by removing the solvent, and by providing the resin composition in the rear stage of the blue light emitting diode, it is possible to produce a laser diode illumination which converts blue light irradiated from the blue light emitting diode to the resin molded body into green light or red light and emits white light.

[ Industrial Applicability ]

According to the present invention, a composition containing 2 perovskite compounds and showing 2 luminescence peaks can be provided. Further, a film, a laminated structure, and a display can be provided using the composition.

Description of the reference numerals

1a 8230, 1b 8230, 2 nd laminated structure 10 8230, film 20 8230, 1 st substrate 21 8230, 2 nd substrate 22 8230, sealing layer 2 8230, light emitting device 3 8230, display, 30 light source 40 8230, liquid crystal panel 50 8230, prism sheet 60 8230, light guide plate

Claims

1. A composition having a luminescent property, which contains the following component (1), the following component (1) -1 and the following component (2), and the mass ratio (1)/(2) of the component (1) to the component (2) is 0.001 to 1;

A is a component located at each vertex of a hexahedron centered on B in the perovskite crystal structure, is a cation having a valence of 1,

x represents a component located at each vertex of an octahedron centering on B in the perovskite crystal structure, and is at least 1 anion selected from halide ions and thiocyanate ions,

b is a component located at the center of a hexahedron with a at the apex and an octahedron with X at the apex in the perovskite crystal structure, and is a metal ion;

A difference between an emission peak wavelength of the component (1) -1 and an emission peak wavelength of the component (1) is 70nm to 140 nm;

(2) The components: an addition polymerizable compound having an ionic group, or a polymer obtained by self-polymerization of 1 kind of the addition polymerizable compound having an ionic group.

2. The composition according to claim 1, wherein the component (2) is a radical polymerizable compound or an ion polymerizable compound, or a polymer thereof.

3. The composition according to claim 1, wherein the addition polymerizable compound having an ionic group is at least one selected from the group consisting of acrylates having an ionic group and derivatives thereof, methacrylates having an ionic group 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 (2) form an aggregate.

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

(3) The components: solvent(s)

(4) The components: a polymerizable compound or a polymer thereof.

6. The composition according to any one of claims 1 to 3, further comprising the following (4'); (1) The total content ratio of the component (2) and the component (4') is 90% by mass or more relative to the total mass of the composition;

(4') component (A): a polymer.

7. The composition according to any one of claims 1 to 3, which further comprises the following component (5),

(5) The components: at least 1 selected from ammonia, amines and carboxylic acids, and salts or ions thereof.

8. The composition according to any one of claims 1 to 3, further comprising the following component (6),

(6) The components: 1 or more compounds selected from the group consisting of organic compounds having an amino group, an alkoxy group, and a silicon atom, and silazanes or modified forms thereof.

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

10. A film using the composition according to any one of claims 1 to 9.

11. A laminated structure comprising the film of claim 10.

12. A light-emitting device comprising the laminated structure according to claim 11.

13. A display device comprising the laminated structure according to claim 11.

14. A method of making a composition, comprising:

a step of dispersing the following component (1) in the following component (3) to obtain a dispersion liquid;

mixing the obtained dispersion with the following component (2') to obtain a mixed solution;

a step of obtaining a mixed solution of polymers containing 1 type of addition polymerizable compound having an ionic group by subjecting the obtained mixed solution to a polymerization treatment;

mixing the obtained mixed solution containing the 1 kinds of polymers of addition polymerizable compounds having ionic groups with the following component (4);

mixing the following (1) -1 components with the obtained mixed solution containing the component (4);

the mass ratio (1)/(2 ') of the component (1) to the component (2') is 0.001 to 1;

b is a component located at the center of a hexahedron having A at the apex and an octahedron having X at the apex in the perovskite crystal structure, and is a metal ion,

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

The difference between the emission peak wavelength of the component (1) -1 and the emission peak wavelength of the component (1) is 70nm to 140nm,

(2') component (A): addition polymerizable compound having ionic group

(3) The components: solvent(s)

(4) The components: a polymerizable compound or a polymer thereof.