TW201906985A - Composition, film, laminated structure, light-emitting device, display, and method of manufacturing the same - Google Patents

Abstract

The present invention relates to a composition having luminescent properties comprising (1) and (2), wherein (1) is a compound having a perovskite crystal structure, said compound comprising A ions, B ions, X ions, and (2) is an addition polymerization compound having an ionic group or a reformed product thereof, and wherein: the A ions are monovalent cations, and from hexahedrons in the perovskite type crystal structure with the A ions being located respective vertexes thereof while the B ions being located at respective centers thereof; the B ions are metal ions; the X ions are at least one type of anions selected from the group consisting of halogen ions and thiocyanate ions, and form octahedrons in the perovskite type crystal structure with the X ions being position at respective vertexes thereof while the B ions being located at respective centers thereof.

Description

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

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

This application claims the priority of Japanese Patent Application No. 2017-123597 filed in Japan on June 23, 2017, and uses its content in this case.

An LED backlight equipped with a blue LED and a composition containing two compounds having different emission wavelengths has been developed. In recent years, as a luminous compound contained in the aforementioned composition, attention has also been paid to perovskite compounds.

For example, as a composition containing a perovskite compound, there have been reports of a composition in which two layers are formed by containing different perovskite compounds in each layer (Non-Patent Document 1).

    [Prior technical literature]         [Non-patent literature]    

[Non-Patent Literature 1] Xiaoming Li, Ye Wu, Shengli Zhang, Bo Cai, Yu Gu, Jizhog Song, Haibo Zeng, Adv. Funct. Mater., 26, 2435-2445 (2016)

However, since the composition formed by lamination described in the above-mentioned Non-Patent Document 1 requires a step for forming a plurality of layers, productivity cannot be said to be satisfactory.

Therefore, the present inventors have thought that if a plurality of perovskite compounds are used to form a layer to obtain light with different emission wavelengths, the number of steps can be reduced and productivity can be improved. Two types of mixtures with different emission wavelengths can be manufactured. Composition of perovskite compounds.

In this discussion, when measuring the emission wavelength of the obtained composition, a new problem was faced, that is, the intrinsic emission wavelength of each perovskite compound disappeared, and the intrinsic emission wavelength of each of the perovskite compounds was emitted. Different light with new emission wavelength.

The present invention has been made in view of the above-mentioned subject, and an object thereof is to provide a composition and a method for manufacturing the same, and a film, a laminated structure, a light-emitting device, and a display using the composition, wherein the composition is a plurality of types having different emission wavelengths Mixing the perovskite compounds can also maintain the composition of the emission wavelength inherent to each perovskite compound.

As a result of intensive studies to solve the above problems, the present inventors have found that a composition containing a perovskite compound, an addition polymerizable compound having an ionic group, or a polymer thereof is mixed with a plurality of perovskite compounds to The resulting composition can maintain the emission wavelength inherent to each perovskite compound.

That is, the embodiments of the present invention are inventions including the following [1] to [17].

[1] A composition comprising a light-emitting composition containing the following (1) component and the following (2) component; wherein

(1) Component: A perovskite compound containing A, B, and X as constituent components (A is a component of each vertex of a hexahedron with B as a center in a perovskite-type crystal structure, and is 1 X is a component of each apex of an octahedron with B as the center in the perovskite crystal structure, and X is at least 1 selected from the group consisting of halide ions and thiocyanate ions. Anion; B, which is a metal ion in the center of the hexahedron in which A is arranged at the vertex and the octahedron in which X is arranged at the vertex, in the perovskite-type crystal structure.)

(2) Component: An addition polymerizable compound or an polymer thereof having an ionic group.

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

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

[4] The composition item 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) is formed as an aggregate.

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

(3) Ingredient: solvent

(4) Component: a polymerizable compound or a polymer thereof.

[6] The composition according to any one of [1] to [4], further comprising a component selected from the following (4 '), with respect to the total mass of the composition, (1) component, (2 ) And the total content ratio of the component (4 ') is 90% by mass or more;

(4 ') Component: polymer.

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

(5) Ingredient: at least one selected from the group consisting of ammonia, amines and carboxylic acids, and salts or ions thereof.

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

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

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

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

(1) -1 component: A perovskite compound having a light emission peak wavelength different from the component (1).

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

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

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

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

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

(1) Component: A perovskite compound containing A, B, and X as constituent components (A is a component of each vertex of a hexahedron with B as a center in a perovskite-type crystal structure, and is 1 X is a component of each apex of an octahedron with B as the center in the perovskite crystal structure, and X is at least 1 selected from the group consisting of halide ions and thiocyanate ions. An anion; B is a metal ion in the center of a hexahedron in which A is arranged at the vertex and an octahedron in which X is arranged at the vertex in the perovskite-type crystal structure; (2 '): Addition polymerizable compound having an ionic group; (3) component: solvent; (4) component: polymerizable compound or polymer thereof.

[16] The method for producing a composition according to item [15], further comprising the step of mixing the following (1) -1 component in a mixed solution containing the aforementioned (4) component; (1) -1 component: The component (1) is a perovskite compound having a different emission peak wavelength.

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

According to the present invention, a composition and a manufacturing method thereof, and a film, a laminated structure, a light-emitting device, and a display using the composition can be provided. The composition is a mixture of a plurality of perovskite compounds having different emission wavelengths. It can also maintain the composition of the intrinsic emission wavelength of each perovskite compound.

1a‧‧‧The first laminated structure

1b‧‧‧Second layered structure

2‧‧‧light-emitting device

3‧‧‧ Display

10‧‧‧ film

20‧‧‧The first substrate

21‧‧‧ 2nd substrate

22‧‧‧Sealing layer

30‧‧‧ light source

40‧‧‧LCD panel

50‧‧‧ cymbals

60‧‧‧light guide

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

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

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

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

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

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

<Composition>

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

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

(1) Component: A perovskite compound containing A, B, and X as constituent components. Hereinafter, it is described as "(1) component".

A is a monovalent cation in the component of each apex of a hexahedron with B as the center in the perovskite-type crystal structure.

X is a component of each apex of an octahedron with B as the center in the perovskite crystal structure, and it is at least one anion selected from the group consisting of a halide ion and a thiocyanate ion.

B is a component of the perovskite-type crystal structure, and the components located in the center of the hexahedron in which A is arranged at the vertex and the octahedron in which X is arranged at the vertex are metal ions.

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

It is estimated that the composition of the present embodiment can form a protected area near the perovskite compound by containing the component (2). Therefore, when the perovskite compound having a different emission peak wavelength from the component (1) is mixed, the disappearance of the intrinsic luminescence wavelength possessed by each perovskite compound and the difference from the intrinsic luminescence wavelength possessed by each perovskite compound can be suppressed. The occurrence of light with a new emission wavelength. Therefore, it is considered that the emission wavelength inherent to each perovskite compound can be maintained.

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

As long as it is within the range of the effect of the present invention, the form in which the aggregates containing the component (1) and the component (2) are formed is not limited. In the present embodiment, for example, by covering the component (2) with the component (1), an aggregate containing the component (1) and the component (2) can be formed. At the same time, in this embodiment, for example, (1) the components are associated to form aggregates, and the surface of the aggregate may be covered with the component (2) to form an aggregate containing the components (1) and (2). .

That is, it can be considered that a protective region is formed by the component (2) on the surface of the aggregate, and the component (1) and the component (1) -1 of the perovskite compound having a different emission peak wavelength from that described later are suppressed Contact, and the effect of the present invention is obtained.

In the composition of the present embodiment, a method for observing the aggregates containing the component (1) and the component (2) includes, for example, observation of the composition with a scanning electron microscope (SEM) or a transmission electron microscope (TEM). method. The elemental distribution can be analyzed in detail by energy dispersive X-ray analysis (EDX measurement) using SEM or TEM.

For example, the EDX measurement using SEM or TEM confirms that the interface between particles containing the element derived from (1) component is masked by the region containing element derived from (2) and contains aggregates of (1) and (2) Formation.

The shape of the aggregate is not particularly limited. At the same time, as long as the average size of the agglomerates is within the range of the effect of the present invention, the average Ferre diameter of the agglomerates is preferably 0.01 μm to 100 μm, and more preferably 0.02 μm to 20 μm. It is more preferably from 0.05 μm to 2 μm.

The "Ferre path" in this specification refers to the maximum distance between two parallel straight lines that sandwich the observation object (aggregate) on the TEM or SEM image. A method of calculating the average Ferre diameter of the aggregates includes, for example, a method of observing more than 20 aggregates by SEM or TEM, and taking an average value thereof. More specifically, for example, 20 aggregates can be observed by SEM or TEM, and the average Ferre diameter of the aggregates can be obtained by averaging the aggregates.

Since the average Ferre diameter of the aggregate is equal to or more than the above-mentioned lower limit value, a protective area is formed near the component (1), and when a plurality of perovskite compounds having different emission peak wavelengths from the component (1) are mixed, it can be prevented The disappearance of the inherent emission wavelengths possessed by the respective perovskite compounds, and the generation of new emission wavelengths different from the intrinsic emission wavelengths possessed by the respective perovskite compounds. Therefore, the emission wavelength inherent to each perovskite compound can be maintained more. At the same time, since the average Ferre diameter of the aggregate is equal to or less than the above-mentioned upper limit value, the dispersibility to the solvent or resin can be improved. The "plurality of perovskite compounds" in this embodiment means two or more perovskite compounds, and two kinds of perovskite compounds are preferred. When two kinds of perovskite compounds are contained, it is preferable that the component (1) -1 contains a perovskite compound having a light emission peak wavelength different from the component (1) and the component (1).

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

(1) -1 component: A perovskite compound having a light emission peak wavelength different from the component (1).

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

It is considered that even if the aggregates of (1) and (2) components are associated with the aggregates of (1) -1 and (2) components, (1), (2), and (1) -1 are formed. When the components are aggregated, the interface of (1) component and (1) -1 component still has (2) a protected area formed by the component, and the present invention is obtained when the contact between (1) component and (1) -1 component is suppressed Effect.

Meanwhile, in terms of maintaining visible light transmittance, the average Ferre diameter of the aggregates of the components (1) -1 and (2) is preferably 20 μm or less. As a method of calculating the average Ferre diameter of the aggregates of the components (1) -1 and (2), a method of calculating the average Ferre diameter of the aggregates of the components (1) and (2) can be mentioned.

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

(3) Ingredient: solvent. Hereinafter, it will be described as "(3) component".

(4) Component: a polymerizable compound or a polymer thereof. However, those contained in the aforementioned (2) component are removed. Hereinafter, it is described as "(4) component."

In the composition of the present embodiment, the component (1) is preferably at least one of a group consisting of components (3) and (4).

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

(5) Ingredient: at least one compound or ion selected from the group consisting of ammonia, amines and carboxylic acids, and salts or ions thereof. It is described below as "(5) component."

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

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

In the present specification, the "modified product of silazane" refers to a compound produced by the modification treatment of silazane. The modification processing method is described later.

The composition of this embodiment may have components other than the components (1) to (6) described above.

Other components include, for example, a number of impurities, a compound having an amorphous structure formed from an elemental component constituting a perovskite compound, and a polymerization initiator.

As for the total mass of the composition, the content of other components is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 1% by mass or less.

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

(4 ') Component: polymer.

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

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

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

(1) The component (2) and the component (2) are indispensable components, and a composition containing at least one selected from the group consisting of the components (3) and (4) is further included in the composition with respect to the total of the composition. The content ratio of the component (1) is not particularly limited as long as it has the effect of the present invention. In the composition of this embodiment, from the viewpoint that it is not easy to aggregate the perovskite compound, and from the viewpoint of preventing concentration quenching, the upper limit and lower limit of the content ratio of the component relative to the total mass of the composition (1), It is preferably within the following range.

Specifically, the upper limit is preferably 50% by mass or less, more preferably 1% by mass or less, and even more preferably 0.5% by mass or less. Meanwhile, in terms of obtaining a good quantum yield, the aforementioned lower limit value is preferably 0.0001% by mass or more, more preferably 0.0005% by mass or more, and more preferably 0.001% by mass or more.

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

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

(1) The component content ratio with respect to the total mass of the composition is preferably 0.0001% by mass to 1% by mass, more preferably 0.0005% by mass to 1% by mass, and more preferably 0.001% by mass to 0.5% by mass. Even better.

In the composition of this embodiment, the composition in which the content ratio of the (1) component to the total mass of the composition is within the above range is preferable because the component (1) does not easily aggregate and exhibits high luminescence. .

(1) The component (2) and the component (2) are indispensable components, and a composition containing at least one selected from the group consisting of the components (3) and (4) is further included in the composition with respect to the total of the composition. The content ratio of the component (2) is not particularly limited as long as it has the effect of the present invention. In the composition of this embodiment, from the viewpoint of stably dispersing the component (1) among the components (3) and (4), the upper limit of the content ratio of the component (2) relative to the total mass of the composition and The lower limit is preferably in the following range.

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

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

The (2) component content ratio with respect to the total mass of the composition is usually 0.001% by mass or more and 50% by mass or less.

(2) The component content ratio with respect to the total mass of the composition is preferably 0.01 mass% to 30 mass%, more preferably 0.1 mass% to 10 mass%, and more preferably 0.3 mass% to 5 mass%. The following is even better.

In the composition of this embodiment, the component (2) whose content ratio is within the above range with respect to the total mass of the composition, the component (1) is stably dispersed in the components (3) and (4) From a viewpoint, it is preferable that the composition formed by mixing a plurality of perovskite compounds can maintain the intrinsic emission wavelength of each perovskite compound.

(1) The component (2) and the component (2) are indispensable components, and a composition containing at least one selected from the group consisting of the components (3) and (4) is further included in the composition with respect to the total of the composition. The mass, the total content ratio of the (1) component and (2) component are not particularly limited as long as they have the effect of the present invention.

In this embodiment, from the viewpoint of making the perovskite compound difficult to aggregate and the prevention of concentration quenching, the total content ratio of the (1) component and (2) component to the total mass of the composition is as follows The range is better.

Specifically, the aforementioned upper limit value is preferably 60% by mass or less, more preferably 40% by mass or less, more preferably 30% by mass or less, and even more preferably 20% by mass or less. Meanwhile, from the viewpoint of obtaining a good quantum yield, it is preferably 0.0002 mass% or more, more preferably 0.002 mass% or more, and more preferably 0.005 mass% or more.

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

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

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

In the composition of this embodiment, the total content of (1) component and (2) component is within the above range with respect to the total mass of the composition, so that (1) component does not easily aggregate and can be good It is better to make use of the luminous point.

It contains (1) component, (2) component, and (4 ') component as a necessary structure, and the total content ratio containing (1) component, (2) component, and (4') component with respect to the total mass of the said composition is In the composition of the embodiment of 90% by mass or more, the (1) component content ratio with respect to the total mass of the composition is not particularly limited as long as it has the effect of the present invention. In this embodiment, from the viewpoint of making the (1) component difficult to aggregate and the prevention of concentration quenching, the content of the (1) component relative to the total mass of the composition is preferably 50% by mass or less. It is more preferably 1% by mass or less, and even more preferably 0.5% by mass or less.

At the same time, from the viewpoint of obtaining good luminous intensity, the content ratio of the component (1) with respect to the total mass of the composition is preferably 0.0001 mass% or more, more preferably 0.0005 mass% or more, and 0.001 mass. More than% is better.

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

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

(1) The content ratio of the component with respect to the total mass of the composition is preferably 0.0001 mass% to 1 mass%, more preferably 0.0005 mass% to 1 mass%, and more preferably 0.001 mass% to 0.5 mass%. The following is even better.

In the composition of the present embodiment, the composition in which the content ratio of the component (1) with respect to the total mass of the composition is within the above-mentioned range is preferable because it can exhibit good luminous properties.

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

At the same time, in a composition in which a plurality of perovskite compounds are mixed, from the viewpoint of maintaining the intrinsic light emission wavelength of each perovskite compound, the (2) component content ratio with respect to the total mass of the composition is It is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, and even more preferably 0.1% by mass or more.

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

The (2) component content ratio with respect to the total mass of the composition is usually 0.001% by mass or more and 50% by mass or less.

(2) The component content ratio with respect to the total mass of the composition is preferably 0.01 mass% to 30 mass%, more preferably 0.1 mass% to 10 mass%, and more preferably 0.3 mass% to 5 mass%. The following is even better.

In the composition of the present embodiment, the composition in which the content ratio of the component (2) with respect to the total mass of the composition is within the above range is based on the viewpoint that the component (1) can be stably dispersed in the component (4 '). In addition, it is preferable that a composition obtained by mixing a plurality of kinds of perovskite compounds can maintain the intrinsic emission wavelength of each perovskite compound.

Contains (1) component, (2) component, and (4 ') component as essential constituents. The total content ratio of (1) component, (2) component, and (4') component is 90 mass relative to the total mass of the aforementioned composition. In the composition of% or more in the embodiment, there is no particular limitation on the total content ratio of the component (1) and (2) with respect to the total mass of the composition. In this embodiment, from the viewpoint of making the (1) component difficult to aggregate and the prevention of concentration quenching, the total content ratio of the (1) component and (2) component relative to the total mass of the composition is based on It is preferably 60% by mass or less, and more preferably 40% by mass or less, more preferably 30% by mass or less, and even more preferably 20% by mass or less. Meanwhile, from the viewpoint of obtaining a good quantum yield, 0.0002 mass% or more is preferable, 0.002 mass% or more is more preferable, and 0.005 mass% or more is more preferable.

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

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

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

In the composition of this embodiment, a composition having a total content ratio of (1) component and (2) component with respect to the total mass of the composition is within the above range, and is preferably a point that exhibits good light emission properties.

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

≪ (1) Ingredients≫

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

The perovskite compound contained in the composition of the present embodiment is a compound having a perovskite crystal structure with A, B, and X as constituents.

A is a monovalent cation in the component of each apex of a hexahedron with B as the center in the perovskite-type crystal structure.

The X system represents a component located at each vertex of an octahedron with B as a center in the perovskite crystal structure, and is at least one anion selected from the group consisting of a halide ion and a thiocyanate ion.

B is a component of the perovskite-type crystal structure, and the components located in the center of the hexahedron in which A is arranged at the vertex and the octahedron in which X is arranged at the vertex are metal ions.

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

In a three-dimensional structure, the composition formula of the perovskite compound is expressed as ABX _{(3 + δ)} .

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

Here, δ is a number which can be appropriately changed in accordance with the charge balance of B, and is -0.7 or more and 0.7 or less.

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

ABX _{(3 + δ)} (-0.7 ≦ δ ≦ 0.7) ... (1)

A is a monovalent cation in the perovskite-type crystal structure, and the component at each vertex of the hexahedron with B as the center.

The X-series represents a component located at each vertex of an octahedron with B as a center in the perovskite-type crystal structure, and is one or more kinds of anions selected from the group consisting of a halide ion and a thiocyanate ion.

B is a component of the perovskite-type crystal structure, and the components located in the center of the hexahedron in which A is arranged at the vertex and the octahedron in which X is arranged at the vertex are metal ions.

[A]

In the perovskite compound, A is a component located at each vertex of a hexahedron with B as the center in the perovskite crystal structure, and is a monovalent cation.

Examples of the monovalent cation include cesium ions, organic ammonium ions, and sulfonium ions. In the perovskite compound, when A is a cesium ion, an organic ammonium ion having 3 or less carbon atoms, or a sulfonium ion having 3 or less carbon atoms, the perovskite compound usually has a three-dimensional representation of ABX _{(3 + δ)} structure.

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

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

In the general formula (A3), R ⁶ to R ⁹ each independently represent a hydrogen atom, an alkyl group which may have an amine group as a substituent, or a cycloalkyl group which may have an amine group as a substituent. However, R ⁶ to R ^{9 are} not hydrogen atoms at the same time.

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

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

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

The number of carbon atoms of the cycloalkyl group represented by R ⁶ to R ⁹ is usually independently 3 to 30, preferably 3 to 11, and more preferably 3 to 8. The number of carbon atoms is the number of carbon atoms including a substituent.

The groups represented by R ⁶ to R ⁹ 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 (A3) and reducing the number of carbon atoms of the alkyl groups and cycloalkoxy groups, it is possible to obtain a three-dimensional light emitting light having a high light intensity. Structured compound with perovskite crystal structure.

When the number of carbon atoms of the alkyl group or cycloalkyl group is 4 or more, a compound having a 2-dimensional and / or quasi-2D (quasi-2D) perovskite crystal structure can be obtained in part or all. When the 2-dimensional perovskite-type crystal structure is an infinite stack, a 3-dimensional perovskite-type crystal structure can be formed (Reference: PPBoxi et al., J. Phys. Chem. Lett. 2016, 6, 898-907 Wait).

The total number of carbon atoms contained in the alkyl group represented by R ⁶ to R ⁹ is preferably 1 to 4, and the total number of carbon atoms contained in the cycloalkyl group represented by R ⁶ to R ⁹ is 3 to 4 Better. It is preferable that one of R ⁶ to R ⁹ is an alkyl group having 1 to 3 carbon atoms, and 3 of R ⁶ to R ⁹ is a hydrogen atom.

Examples of the alkyl group of R ⁶ to R ⁹ include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, third butyl, and n-pentyl. , Isopentyl, neopentyl, tertiary pentyl, 1-methylbutyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, 2,2-dimethylbutyl, 2 , 3-dimethylbutyl, n-heptyl, 2-methylhexyl, 3-methylhexyl, 2,2-dimethylpentyl, 2,3-dimethylpentyl, 2,4- Dimethylpentyl, 3,3-dimethylpentyl, 3-ethylpentyl, 2,2,3-trimethylbutyl, n-octyl, isooctyl, 2-ethylhexyl, Nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, cetyl, heptadecyl, octadecyl, undecyl , Eicosyl.

Examples of the cycloalkyl group of R ⁶ to R ⁹ each independently form a ring with an alkyl group having 3 or more carbon atoms exemplified in the alkyl group of R ⁶ to R ^9. Examples of the cycloalkyl group include cyclopropyl, Cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, norbornyl, isobornyl, 1-adamantyl, 2-adamantyl, tricyclodecyl Base etc.

The organic ammonium ion represented by A is CH ₃ NH ₃ ⁺ (also called methyl ammonium ion), C ₂ H ₅ H ₃ ⁺ (also called ethyl ammonium ion), or C ₃ H ₇ NH ₃ ⁺ ( also known as propyl ammonium ion) is preferable, and is CH ₃ NH ₃ ⁺ or C ₂ H ₅ H ₃ ⁺ better, and to the CH ₃ NH ₃ ⁺ and better.

Examples of the sulfonium ion represented by A include a sulfonium 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 to R ¹³ each independently represent a hydrogen atom, an alkyl group which may have an amine group as a substituent, or a cycloalkyl group which may have an amine group as a substituent.

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

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

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

The number of carbon atoms of the cycloalkyl group represented by R ¹⁰ to R ¹³ is usually independently 3 to 30, preferably 3 to 11, and more preferably 3 to 8. The number of carbon atoms is the number of carbon atoms including a substituent.

Specific examples of the alkyl group of R ¹⁰ to R ¹³ are each independently an alkyl group exemplified in R ⁶ to R ⁹ .

Specific examples of the cycloalkyl group of R ¹⁰ to R ¹³ are each independently a cycloalkyl group exemplified in R ⁶ to R ⁹ .

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

By reducing the number of alkyl groups and cycloalkyl groups contained in the general formula (A4) and reducing the number of carbon atoms of the alkyl groups and cycloalkyl groups, a perovskite having a three-dimensional structure with high light emission intensity can be obtained. Compound.

When the number of carbon atoms of the alkyl group or cycloalkyl group is 4 or more, a compound having a two-dimensional and / or quasi-two-dimensional perovskite crystal structure can be obtained in part or all. Meanwhile, the total number of carbon atoms contained in the alkyl group represented by R ¹⁰ to R ¹³ is preferably 1 to 4, and the total number of carbon atoms contained in the cycloalkyl group represented by R ¹⁰ to R ¹³ is 3 to 4 Better. R ¹⁰ is an alkyl group having 1 to 3 carbon atoms, and R ¹¹ to R ¹³ are more preferably a hydrogen atom.

[B]

In the perovskite compound, B is a metal ion in the perovskite-type crystal structure, and the component is located at the center of a hexahedron in which A is arranged at the vertex and the center of 8 faces in which X is arranged at the vertex. The metal ion of the component B may be one or more metal ions selected from the group consisting of a monovalent metal ion, a divalent metal ion, and a trivalent metal ion. B is preferably a divalent metal ion, and more preferably contains one or more metal ions selected from the group consisting of lead and tin.

[X]

In the perovskite compound, X is a component represented at the position of each vertex of the octahedron with B as the center in the perovskite crystal structure, and is selected from the group consisting of halide ions and thiocyanate ions. Group of at least 1 anion. 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 in accordance with a desired emission wavelength, and for example, X may contain a bromide ion.

When X is two or more kinds of halide ions, the content ratio of the halide ions may be appropriately selected depending on the emission wavelength, and may be a combination of a bromide ion and a chloride ion or a combination of a bromide ion and an iodide ion, for example.

When the perovskite compound has a three-dimensional structure, it has a three-dimensional network of a common vertex octahedron with B as the center, its vertices set to X, and BX ₆ as the center.

When the perovskite compound has a two-dimensional structure, by setting B as the center and setting the vertices to X, sharing the X of the four vertices of the octahedron represented by BX ₆ as the same plane to form a two-dimensional BX The layer of _{6 and} the layer containing A are laminated with each other.

B is a metal cation that can coordinate to X octahedron.

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

When the compound has a perovskite-type crystal structure with the aforementioned three-dimensional structure, the position of 2θ = 12 to 18 ° in the X-ray diffraction pattern usually confirms the peak from (hk1) = (001) or 2θ = 18 to 25 The position at ° confirms the peak from (hk1) = (110). The position from 2θ = 13 to 16 ° confirms that the peak from (hk1) = (001) or the position from 2θ = 20 to 23 ° confirms that the peak from (hk1) = (110) is better.

When the compound has a perovskite-type crystal structure with the aforementioned two-dimensional structure, the peak from (hk1) = (002) can be confirmed at the position of 2θ = 1 to 10 ° in the X-ray diffraction pattern, and 2θ = 2 The position to 8 ° confirmed that the peak from (hk1) = (002) was better.

Specific examples of compounds which are perovskite compounds and have a three-dimensional structure of a perovskite crystal structure represented by ABX _{(3 + δ)} include CH ₃ NH ₃ PbBr ₃ , CH ₃ NH ₃ PbCl ₃ , CH ₃ NH ₃ PbI ₃ , CH ₃ NH ₃ PbBr _(3-y) I _y (0 <y <3), CH ₃ NH ₃ PbBr _(3-y) Cl _y (0 <y <3), (H ₂ N = CH-NH ₂ ) PbBr ₃ , (H ₂ N = CH-NH ₂ ) PbCl ₃ , (H ₂ N = CH-NH ₂ ) PbI ₃ , CH ₃ NH ₃ Pb _(1-a) Ca _a Br ₃ ( 0 <a ≦ 0.7), CH ₃ NH ₃ Pb _(1-a) Sr _a Br ₃ (0 <a ≦ 0.7), CH ₃ NH ₃ Pb _(1-a) La _a Br _{(3 + δ)} (0 < a ≦ 0.7, 0 <δ ≦ 0.7), CH ₃ NH ₃ Pb _(1-a) Ba _a Br ₃ (0 <a ≦ 0.7), CH ₃ NH ₃ Pb _(1-a) Dy _a Br _{(3 + δ )} (0 <a ≦ 0.7, 0 <δ ≦ 0), 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 <δ ≦ 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 ) Zn _a Br _{(3 -y)} Cl _y (0 <a ≦ 0.7, 0 <y <3) and the like are preferable. In one aspect of the present invention, it is a perovskite compound, a compound having a three-dimensional structure of a perovskite crystal structure represented by ABX _{(3 + δ), and is} represented by CsPbBr ₃ , CsPbBr _(3-y) I _y (0 <y <3) is better.

A specific example of a perovskite compound, a compound having a two-dimensional perovskite crystal structure represented by A ₂ BX _{(4 + δ)} , (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 are preferable.

‧Emission Spectrum

Perovskite compounds are luminous bodies that emit fluorescence in the visible wavelength region.

When X is a bromide ion, the perovskite compound is generally above 480 nm, preferably above 500 nm, more preferably above 510 nm, and usually below 700 nm, preferably below 600 nm, and more preferably within a wavelength range of below 580 nm. Fluorescent light with a peak of maximum luminous intensity.

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

In another aspect of the present invention, when the system X is a bromide ion, the perovskite compound is generally 480 nm to 700 nm, preferably 500 nm to 600 nm, and more preferably in the wavelength range of 510 nm to 580 nm. Extreme peak fluorescence.

When X is an iodide ion, the perovskite compound is usually above 520nm, preferably above 530nm, more preferably above 540nm, and usually below 800nm, preferably below 750nm, and more preferably below 730nm. Fluorescent light with a peak of maximum luminous intensity.

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

In another aspect of the present invention, when the system X is an iodide ion, the perovskite compound is usually 520 nm to 800 nm, preferably 530 nm to 750 nm, and more preferably in the wavelength range of 540 nm to 730 nm. Extreme peak fluorescence.

When X is a chloride ion, it is usually above 300 nm and preferably above 310 nm, more preferably above 330 nm, and usually below 600 nm, preferably below 580 nm, and more preferably below 550 nm. The range can emit fluorescence with a peak of maximum luminous intensity.

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

In another aspect of the present invention, when system X is a chloride ion, the perovskite compound may generally be 300 nm to 600 nm, preferably 310 nm to 580 nm, and may emit in a wavelength range of 330 nm to 550 nm. Fluorescence with extremely high luminous intensity.

The average particle diameter of the component (1) contained in the composition of this embodiment is not particularly limited as long as it has the effect of the present invention. In the composition of the present embodiment, the average particle diameter is preferably 1 nm or more, more preferably 2 nm or more, and even more preferably 3 nm or more from the viewpoint of maintaining the crystal structure of the component (1) well. Meanwhile, in the composition of this embodiment, from the viewpoint of making it difficult to settle the component (1), the average particle diameter of the component (1) is preferably 10 μm or less, more preferably 1 μm or less, and 500 nm or less. Even better.

The above upper limit value and lower limit value can 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 that the (1) component in the composition is difficult to settle and that the crystal structure can be well maintained In other words, the average particle diameter is preferably from 1 nm to 10 μm, more preferably from 2 nm to 1 μm, and even more preferably from 3 nm to 500 nm.

The average particle diameter of the component (1) contained in the composition can be measured by, for example, SEM or TEM. Specifically, the Fischer diameter of the 20 (1) components contained in the composition can be observed by TEM or SEM, and the average Fischer diameter of these can be calculated to obtain the average particle diameter.

The median diameter (D ₅₀ ) of the component (1) contained in the composition of this embodiment is not particularly limited as long as it has the effect of the present invention. In the composition of this embodiment, from the viewpoint of maintaining a good crystal structure of the component (1), the median diameter (D ₅₀ ) of the component (1) is preferably 3 nm or more, and more preferably 4 nm or more. Above 5nm is even better. Meanwhile, in the composition of the present embodiment, from the viewpoint of making the (1) component difficult to settle, the median diameter (D ₅₀ ) of the (1) component is preferably 5 μm or less, and more preferably 500 nm or less. It is more preferable to be below 100 nm.

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

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

≪ (1) -1 ingredients≫

(1) -1 component is a perovskite compound having a different emission peak wavelength from the component (1). In this embodiment, the difference between the emission peak wavelength of the component (1) -1 and the emission peak wavelength of the component (1) when measured under the following conditions is preferably 70 nm or more, and more preferably 75 nm or more. Above 80nm is preferred. Meanwhile, it is preferably below 140 nm, more preferably below 135 nm, and even more preferably below 130 nm. The upper limit value and lower limit value of the difference in the emission peak wavelengths can be arbitrarily combined.

In another 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) when measured under the following conditions is preferably 70 nm to 140 nm, and 75 nm to 135 nm. The following is more preferable, and more preferably 80 nm to 130 nm.

‧Measurement conditions

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

≪ (2) ingredients≫

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

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

The addition polymerizable compound having an ionic group, the anionic group include: e.g. -PO group, -OSO _{3 4} ^2- represented by ^- indicates the group, -COO ^- group represented by, and is -OSO ₃ ^- represents a group, -COO ^- group preferably represented by, and to -COO ^- group represented better.

Examples of the cationic group in the addition polymerizable compound having an ionic group include an ammonium group, a primary amine group, a phosphonium group, a sulfonium group, an imidazolium group, and a pyridinium group. Primary amino groups are preferred.

In the addition polymerizable compound having an ionic group, the ionic group may contain one kind or two or more kinds.

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

Counter anion cationic group is not particularly limited, and may include ^{Br -, Cl -, I -} , F - is a halide ion or a carboxylate anion.

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

The addition polymerization can be exemplified by a polymerization in which a terminal double bond or a triple bond in the compound is polymerized or a ring-opening polymerization reaction by 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 polymerized by radical polymerization. It is more preferable to use a radical polymerizable compound having an ionic group.

(Radical polymerizable compound having an ionic group)

Among the addition-polymerizable compounds having an ionic group, the radically polymerizable compound having an ionic group is a compound having an ionic group and reacting with a polymerizable functional group to polymerize, and reacts with a radical Examples of the polymerizable functional group include a vinyl group and a styryl group, an acrylic group, a methacrylic group, and an allyl group of a vinyl group having a substituent, and may be an acrylic group, a styryl group, or a methacrylic group. It may also be styryl or methacrylic.

Among the addition polymerizable compounds having an ionic group, examples of the radical polymerizable compound include acrylates and derivatives thereof, methacrylates and derivatives thereof, styrenes and derivatives thereof, and acrylonitrile And its derivatives, allyl esters and derivatives of organic carboxylic acids, vinyl esters and derivatives of organic carboxylic acids, dialkyl esters of fumaric acid and their derivatives, and dicarboxylic acids of maleic acid Alkyl esters and derivatives thereof, Dialkyl esters of itaconic acid and derivatives thereof, N-vinylamine derivatives of organic carboxylic acids, maleimide and derivatives thereof, terminal unsaturated hydrocarbons and derivatives thereof Etc. and have an ionic group.

Examples of the acrylates and derivatives thereof having an ionic group include methyl acrylate, ethyl acrylate, acrylic-n-propyl, isopropyl acrylate, acrylic-n-butyl acrylate, isobutyl acrylate, and second butyl acrylate. Ester, 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-hydroxyphenylethyl acrylate, N, N-dimethylacrylamide, N, N-di Partial structures such as ethacrylamide and N-propenylmorpholine have ionic groups.

Examples of the methacrylates and their derivatives having an ionic group include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, and methacrylic acid- N-butyl ester, isobutyl methacrylate, second butyl methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate, Isobornyl acrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, methacrylic acid- 3-hydroxypropyl ester, 2-hydroxybutyl methacrylate, 2-hydroxyphenylethyl methacrylate, N, N-dimethylmethacrylamide, N, N-diethylmethyl Partial structures such as acrylamide and N-acrylamidomorpholine have ionic groups.

Examples of styrene and its derivatives having an ionic group include styrene, 2,4-dimethyl-α-methylstyrene, o-methylstyrene, m-methylstyrene, and p-formyl. Styrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 2,6-dimethylstyrene, 3,4-dimethylstyrene, 3,5-dimethyl Styrene, 2,4,6-trimethylstyrene, 2,4,5-trimethylstyrene, pentamethylstyrene, o-ethylstyrene, m-ethylstyrene, p- Ethylstyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, o-bromostyrene, m-bromostyrene, p-bromostyrene, o-methoxystyrene, m-styrene -Methoxystyrene, p-methoxystyrene, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, 2-vinylbiphenyl, 3-vinylbiphenyl, 4-ethylene Biphenyl, 1-vinylnaphthalene, 2-vinylnaphthalene, 4-vinyl-p-triphenyl, 1-vinylanthracene, α-methylstyrene, o-isopropenyl toluene, m-isopropene Toluene, p-isopropenyl toluene, 2,4-dimethyl-α-methylstyrene, 2,3-dimethyl-α-methylstyrene, 3,5- Methyl-α-methylstyrene, p-isopropyl-α-methylstyrene, α-ethylstyrene, α-chlorostyrene, diisopropylbenzene, 4-aminostyrene, etc. The molecular structure has an ionic group.

Examples of the acrylonitrile and its derivative having an ionic group include a part having a ionic group in a structure such as acrylonitrile. Examples of the acrylonitrile and its derivative having an ionic group include those having a ionic group in a part of the structure such as methacrylonitrile.

Examples of vinyl esters and derivatives of organic carboxylic acids having an ionic group include those having a ionic group in a part of their structure, such as vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl benzoate.

Allyl esters of organic carboxylic acids having an ionic group and derivatives thereof include those having a ionic group in a partial structure such as allyl acetate and allyl benzoate.

Examples of the dialkyl fumarate and its derivatives having an ionic group include dimethyl fumarate, diethyl fumarate, diisopropyl fumarate, Fumaric acid di-second butyl ester, fumaric acid diisobutyl ester, fumaric acid di-n-butyl ester, fumaric acid di-2-ethylhexyl ester, fumaric acid Some structures such as diphenyl methyl dibenzoate have ionic groups.

Examples of the dialkyl esters of maleic acid having an ionic group and derivatives thereof include dimethyl maleate, diethyl maleate, diisopropyl maleate, Maleic acid di-second butyl ester, maleic acid diisobutyl ester, maleic acid di-n-butyl ester, maleic acid di-2-ethylhexyl ester, maleic acid Some structures such as diphenyl methyl dibenzoate have ionic groups.

Dialkyl itaconate and its derivatives having an ionic group include dimethyl itaconate, diethyl itaconate, diisopropyl itaconate, and di-dibutyl itaconate Esters, diisobutyl itaconic acid, di-n-butyl itaconic acid, di-2-ethylhexyl itaconic acid, diphenyl methyl itaconic acid and other partial structures have ionic groups.

Examples of the N-vinylamine derivative of an organic carboxylic acid having an ionic group include those having a ionic group in a partial structure such as N-methyl-N-vinylacetamide.

Examples of the maleimide and its derivatives having an ionic group include those having a ionic group in a partial structure such as N-phenyl maleimide and N-cyclohexyl maleimide.

Examples of terminal unsaturated hydrocarbons having ionic groups and derivatives thereof include 1-butene, 1-pentene, 1-hexene, 1-octene, vinylcyclohexane, vinyl chloride, allyl alcohol, etc. Some structures have ionic groups.

Among the addition polymerizable compounds having an ionic group, the radical polymerizable compounds having an ionic group include those in which a part of the hydrogen atoms of the radical polymerizable compound is replaced by the anionic group, or the above Some of the carbon atoms of the radically polymerizable compound are substituted with the aforementioned anionic group.

(Ionic polymerizable compound having an ionic group)

Among the addition polymerizable compounds having an ionic group, the ionic polymerizable compound having an ionic group is a compound having an ionic group and polymerized by reacting cations, anions and the like with a polymerizable functional group, and reacts with an ion. Examples of the polymerizable functional group 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, and organic carboxylic acids. Allyl esters 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, Itaconic Partial structures of dialkyl esters and derivatives of acids, N-vinylamine derivatives of organic carboxylic acids, maleimide and derivatives thereof, terminal unsaturated hydrocarbons and derivatives, and epoxy monomers Those with ionic groups.

Among the addition polymerizable compounds having an ionic group, examples of the ionic polymerizable compound having an ionic group include those in which a part of hydrogen atoms of the ionic polymerizable compound is replaced by the anionic group, or the above-mentioned ionic polymerization. Some of the carbon atoms of the sex compounds are substituted by the aforementioned anionic groups.

Part or all of the aforementioned 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 include a polymerizable compound having an anionic group or a salt having a counter cation, and examples thereof include barium acrylate, 3-sulfopropyl potassium methacrylate, and 3-[[2- (Methacrylic acid) ethyl] dimethylammonium] propionate, 2- (methacrylic acid) ethyl phosphate 2- (trimethylammonium) ethyl ester, 2-acrylic acid Amine-2-methylpropanesulfonic acid, sodium vinylsulfonate, vinylsulfonic acid, sodium p-styrenesulfonate hydrate, sodium 4-vinylbenzenesulfonate, 4-carboxystyrene, 3-allyl Oxypropionic acid, acrylic acid, and methacrylic acid can be acrylic acid, methacrylic acid, 2-acrylamido-2-methylpropanesulfonic acid, 4-carboxystyrene, 3-[[2- (methacrylic acid) (Oxy) ethyl] dimethylammonium] propionate, which may be methacrylic acid, 2-propenylamine-2-methylpropanesulfonic acid, 4-carboxystyrene, 3-[[2- (methyl Methacryloxy) ethyl] dimethylammonium] propionate, which may also be methacrylic acid, 4-carboxystyrene, 3-[[2- (methacryloxy) ethyl] diacetate Methylammonium] propionate.

Among the addition polymerizable compounds having an ionic group, the polymerizable compound having a cationic group or the salt having a counter anion include trimethyl-2-methacryloxyethylammonium chloride and phosphoric acid. 2- (methacryloxy) ethyl 2- (trimethylammonium) ethyl, 3-[[2- (methacryloxy) ethyl] dimethylammonyl] propionate (3-acrylamidopropyl) trimethylammonium chloride, trimethylvinylammonium bromide, 4-vinylbenzylamine, 3-aminopropene hydrochloride, dehydrated glyceryltrimethyl The ammonium chloride may be 4-vinylbenzylamine or 3-[[2- (methacryloxy) ethyl] dimethylammonium] propionate.

The addition polymerizable compound having an ionic group may be a polymer having an ionic group polymerized by a method described later.

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 polymerized by a method described later.

Polymerization refers to the addition of at least a part of polymerizable functional groups such as vinyl, acrylic, methacrylic, allyl, and epoxy groups in addition-polymerizable compounds having an ionic group. The intention is to react with free radicals or ions generated by initiators to form polymers.

Examples of the polymer of an addition polymerizable compound having an ionic group include polystyrene resin, polyethylene resin, polyacrylic resin, polymethacrylic resin, and polyallyl resin containing at least one of the above-mentioned ionic groups. , Epoxy resin.

≪ (3) ingredients≫

(3) The component is a solvent. The solvent is not particularly limited as long as it is a solvent capable of dispersing the component (1), but it is preferable that the component (1) is difficult to dissolve.

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

The term "dispersed" in this specification refers to a state in which (1) components, aggregates, etc. float or are suspended in a solvent, a polymerizable compound, a polymer, or 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; γ-butyrolactone, acetone, dimethyl ketone, and diisocyanate. Ketones such as methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl cyclohexanone; diethyl ether, methyl-third butyl ether, diisopropyl ether, dimethoxymethane, dimethoxyethane, 1, Ethers such as 4-dioxane, 1,3-dioxolane, 4-methyldioxolane, tetrahydrofuran, methyltetrahydrofuran, anisole, phenyl ether, etc .; methanol, ethanol, 1-propane Alcohol, 2-propanol, 1-butanol, 2-butanol, tertiary butanol, 1-pentanol, 2-methyl-2-butanol, methoxypropanol, diacetone alcohol, cyclohexanol , 2-fluoroethanol, 2,2,2-trifluoroethanol, 2,2,3,3-tetrafluoro-1-propanol and other alcohols; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol Glycol ethers such as monobutyl ether, ethylene glycol monoethyl ether acetate, and triethylene glycol dimethyl ether; N-methyl-2-pyrrolidone, N, N-dimethylformamide, acetamidine, N , N-dimethylacetamidine and other organic solvents with amidino group; acetonitrile, isobutyronitrile, propionitrile, methoxyacetonitrile and others with nitrile group Organic solvents; organic solvents with carbonate groups such as ethyl carbonate and propylene carbonate; organic solvents with halogenated hydrocarbon groups such as dichloromethane and chloroform; n-pentane, cyclohexane, n-hexane, benzene, Organic solvents having a hydrocarbon group, such as toluene and xylene; dimethyl fluorene, 1-octadecene, and the like.

Among these solvents, consider esters such as methyl formate, ethyl formate, propyl formate, pentyl formate, methyl acetate, ethyl acetate, and pentyl acetate; γ-butyrolactone, acetone, dimethyl ketone, Ketones such as diisobutanone, cyclopentanone, cyclohexanone, and methylcyclohexanone; diethyl ether, methyl-tertiary butyl ether, diisopropyl ether, dimethoxymethane, dimethoxyethane, Ethers such as 1,4-dioxane, 1,3-dioxolane, 4-methyldioxolane, tetrahydrofuran, methyltetrahydrofuran, anisole, phenylethyl ether, acetonitrile, isobutyronitrile Organic solvents with nitrile groups such as propionitrile, methoxyacetonitrile, etc .; organic solvents with carbonate groups such as ethyl carbonate, propylene carbonate; organic solvents with halogenated hydrocarbon groups such as dichloromethane, chloroform; n-pentyl Organic solvents having a hydrocarbon group such as alkane, cyclohexane, n-hexane, benzene, toluene, xylene, and the like have low polarity and are difficult to dissolve. (1) The component is preferred, and organic solvents having a halogenated hydrocarbon group such as dichloromethane and chloroform are preferred. ; Organic solvents having a hydrocarbon group such as n-pentane, cyclohexane, n-hexane, benzene, toluene, and xylene are more preferred.

≪ (4) ingredients≫

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

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

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

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

For example, when the composition of this embodiment is produced at room temperature and normal pressure, the polymerizable compound other than the component (2) is not particularly limited, but examples thereof include styrene, acrylate, methacrylate, Polymerizable compounds other than the well-known component (2), such as acrylonitrile. Among them, the polymerizable compound other than the component (2) is preferably one or both of acrylates and methacrylates which are monomer components of acrylic resins.

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

For example, when the composition of this embodiment is produced at room temperature and normal pressure, polymers other than the component (2) are not particularly limited, and examples thereof include well-known ones such as polystyrene, acrylic resin, and epoxy resin. polymer. Among these polymers, acrylic resins are preferred. The acrylic resin contains constituent units derived from either or both of acrylate and methacrylate.

In the composition of the present embodiment, for all the constituent units contained in the polymerizable compound or polymer of the component (4), either or both of acrylate and methacrylate, and constituent units derived therefrom. When expressed in mole%, it can be more than 10 mole%, it can be more than 30 mole%, it can be more than 50 mole%, it can be more than 80 mole%, or it can be 100 mole%.

The weight average molecular weight of the aforementioned polymer is preferably from 100 to 1,200,000, more preferably from 1,000 to 800,000, and even more preferably from 5,000 to 150,000.

The "weight average molecular weight" in this specification refers to a polystyrene conversion value measured by a gel permeation chromatography (GPC) method.

≪ (5) ingredients≫

(5) A component is a compound or ion of at least 1 sort (s) chosen from the group which consists of ammonia, an amine, a carboxylic acid, and these salts or ions.

(5) The component includes at least one compound or ion selected from the group consisting of these salts or ions as a form of obtaining ammonia, amine, and carboxylic acid, and the aforementioned compound.

That is, the component (5) includes a group selected from the group consisting of ammonia, amines, carboxylic acids, ammonia salts, amine salts, carboxylic acid salts, ammonia ions, amine ions, and carboxylic acid ions. At least one compound or ion.

Ammonia, amines, and carboxylic acids, as well as these salts or ions, usually function as capping ligands. "End-capped ligand" refers to a compound which has the function of stably dispersing the component (1) in the composition, adsorbed on the surface of the component (1). Examples of the ions of ammonia or amine, or salts (such as ammonium salts) include ammonium cations represented by the following general formula (A1), and ammonium onium salts containing the cations. Examples of ions or salts of carboxylic acids (such as carboxylic acid salts) include carboxylic acid ester anions represented by the general formula (A2) described below, and carboxylic acid salts containing the anions. The composition of the present embodiment may contain either one of an ammonium salt and the like, and a carboxylate salt, or both.

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

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

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

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

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

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

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

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

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

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

The alkenyl group of R ⁴ can be exemplified by a single bond (CC) between any one of carbon atoms in the linear or branched alkyl group as exemplified in R ⁶ to R ⁹ (C = C), the position of the double bond is not limited.

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

The preferred embodiment is a halide ion, a carboxylate ion, or the like ^- when the ammonium cation to form a salt, the counter anion is not particularly limited, may include ^{Br -, Cl -, I -} , F.

Preferred examples of the ammonium onium cation represented by the general formula (A1) and the ammonium onium salt having a counter anion include n-octyl ammonium salts and oleyl ammonium salts.

(5) The component may be a carboxylic acid ester anion represented by the general formula (A2) or a carboxylic acid salt containing the ion.

R ⁵ -CO ₂ ^- ‧‧‧ (A2)

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

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

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

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

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

R ⁵ is preferably an alkyl group or an unsaturated hydrocarbon group. The unsaturated hydrocarbon group is preferably an alkenyl group.

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

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

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

The carboxylic acid ester 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 examples thereof include alkali metal cations, alkaline earth metal cations, and ammonium cations.

≪ (6) ingredients≫

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

(Organic compounds with amine, alkoxy and silicon atoms)

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

The organic compound having an amine group, an alkoxy group, and a silicon atom may not contain any one or both of an ionic group and an addition polymerizable group.

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

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

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

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

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

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

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

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

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

Examples of the alkoxy group of R ²⁵ to R ²⁶ include a methoxy group, an ethoxy group, and a butoxy group, and a methoxy group is preferred.

The divalent hydrocarbon group represented by A may be a group obtained by removing two hydrogen atoms from a hydrocarbon compound. 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 amine 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.

Organic compounds having an amine group, an alkoxy group, and a silicon atom represented by the general formula (A5-5) are trimethoxy [3- (methylamino) propyl] silane, and 3-aminopropyltriethyl Oxysilane, 3-aminopropyldimethoxymethylsilane, 3-aminopropyldiethoxymethylsilane, 3-aminopropyltrimethoxysilane are preferred, and 3-amine Phenylpropyltrimethoxysilane is more preferred.

The organic compound having an amine group, an alkoxy group, and a silicon atom is an organic compound represented by the aforementioned general formula (A5-5), wherein R ²² and R ²³ are hydrogen atoms, R ²⁴ is the aforementioned alkyl group, R ²⁵ and R ²⁶ is preferably an alkoxy compound.

(Silazane or its modification)

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

Silazane is a compound having a Si-N-Si bond.

The silazane may have any of linear, branched, or cyclic shapes. Meanwhile, the silazane may be a low molecule or a high polymer (also referred to as polysilazane in this specification).

In this manual, "low-molecular silazane" refers to silazane with an average molecular weight of less than 600, and "polymer silazane (polysilazane)" refers to those with an average molecular weight of 600 or more and 2,000 or less. Silazane.

In the present specification, the "number average molecular weight" refers to a polystyrene conversion value that can be measured by a gel permeation chromatography (GPC) method.

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

Silazane can be modified by using the method described below.

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

Modification refers to the Si-N-Si bond contained in at least a part of the silazane, and the substitution of N with O to form a Si-O-Si bond. The modified product of silazane contains Si-O. -Si bond compounds.

The modified product of silazane has, for example, the above-mentioned low-molecular compound containing at least one N substituted by O in the general formula (B1) or (B2) and a structure represented by the general formula (B3) A polymer compound in which at least 1 N of the unit polysilazane is substituted with O, or a polymer compound in which at least 1 N is substituted in a polysilazane having a structure represented by the general formula (B4) Better.

The proportion of the number of substituted O with respect to the total amount of N contained in the general formula (B2) is preferably 0.1 to 100%, more preferably 10 to 98%, and 30 to 95%. Better.

The proportion of the number of substituted O with respect to the total amount of N contained in the general formula (B3) is preferably 0.1 to 100%, more preferably 10 to 98%, and 30 to 95%. Better.

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

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

The number of Si atoms, N atoms, and O atoms contained in silazane and its modified substances can be determined by nuclear magnetic resonance spectroscopy (NMR), X-ray photoelectron spectroscopy (XPS), or by transmission electron microscopy (TEM) Calculated by energy dispersive X-ray analysis (EDX).

A particularly preferable method is calculated by measuring the number of Si atoms, N atoms, and O atoms in the composition by X-ray photoelectron spectroscopy (XPS).

The ratio of the number of O atoms to the number of N atoms contained in the silazane and its modified substance determined by the above method is preferably 0.1 to 99%, more preferably 10 to 95%, and 30 to 90%. % Is even better.

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

In the general formula (B1), R ¹⁴ and R ¹⁵ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, or 3 to 20 carbon atoms. Cycloalkyl, aryl having 6 to 20 carbon atoms or alkylsilyl having 1 to 20 carbon atoms. Alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms or 1 or more carbon atoms Alkylsilyl groups below 20 may have substituents such as amine groups. The plural R ¹⁵ may be the same or different.

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

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

The plural R ¹⁴ may be the same or different.

The plural R ¹⁵ may be the same or different.

n represents 1 or more and 20 or less. n may be 1 or more and 10 or less, or may be 1 or 2.

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

Low molecular silazane is preferably octamethylcyclotetrasilazane and 1,3-diphenyltetramethyldisilazane, and octamethylcyclotetrasilazane is more preferred.

Polysilazane is a polymer compound having a Si-N-Si bond. Although not particularly limited, a polymer compound having a structural unit represented by the following general formula (B3) can be mentioned. The structural unit represented by the general formula (B3) contained in the polysilazane may be one type or plural types.

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

The plural R ¹⁴ may be the same or different.

The plural R ¹⁵ may be the same or different.

m is an integer representing 2 to 10,000.

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

Meanwhile, the polysilazane having a structural unit represented by the general formula (B3) may be, for example, an organic polysilazane in which at least one R ¹⁵ is a group other than a hydrogen atom. It can be used with suitable choice of perhydropolysilazane and organic polysilazane, or mixed.

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

n ₂ is an integer representing 1 to 10,000. n ₂ may be 1 or more and 10 or less, or may be 1 or 2.

Although silazane or a modified product thereof is not particularly limited, in terms of improving dispersibility and suppressing aggregation, an organic polysilazane or a modified product thereof is preferred. The organic polysilazane may be, for example, an alkyl group having at least one of R ¹⁴ and R ¹⁵ in the general formula (B3) having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, or carbon. Organic polysilicon nitrogen having a structural unit represented by a general formula (B3), a cycloalkyl group having 3 to 20 atoms, an aryl group having 6 to 20 carbon atoms, or an alkylsilyl group having 1 to 20 carbon atoms alkyl. At the same time, it may contain at least one bonding bond in the general formula (B4) which is bonded to R ¹⁴ or R ^15. At least one of the aforementioned R ¹⁴ and R ¹⁵ is an alkyl group or carbon having 1 to 20 carbon atoms. The general formula (B4) is an alkenyl group having 1 to 20 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. ) Is an organopolysilazane.

The organic polysilazane is an organic polysilazane in which at least one of R ¹⁴ and R ¹⁵ in the general formula (B3) is a methyl group and has a structural unit represented by the general formula (B3), or a general formula (B4 At least one of the bonding bonds in) is bonded to R ¹⁴ or R ^15. At least one of R ¹⁴ and R ¹⁵ is a methyl group and a polysilazane having a structure represented by the general formula (B4) is preferred. Or polysilazane in which at least a part of R ¹⁴ or R ¹⁵ is a methyl group is preferred.

A general polysilazane has a structure having a ring structure such as a linear structure, a 6-membered ring, or an 8-membered ring. As mentioned above, the molecular weight is a number average molecular weight (Mn) of 600 to 2,000 (in terms of polystyrene), and may be a liquid or solid substance depending on the molecular weight. As the polysilazane, commercially available products can be used, and commercially available products include NN120-10, NN120-20, NAX120-20, NN110, NAX120, NAX110, NL120A, NL110A, NL150A, NP110, NP140 (AZ electronic materials Company), and AZNN-120-20, Durazane (registered trademark) 1500 Slow Cure, Durazane (registered trademark) 1500 Rapid Cure, and Durazane (registered trademark) 1800 (Merck Performnce Materials) Durazane (registered trademark) 1033 (Merck Advanced Technology Materials Co., Ltd.) and so on.

Polysilazane having a structural unit represented by the general formula (B3) is preferably AZNN-120-20, Durazane (registered trademark) 1500 Slow Cure, Durazane (registered trademark) 1500 Rapid Cure, and Durazane (registered trademark) ) 1500 Slow Cure is better.

<Preparation ratio of each component>

In the composition of this embodiment, the blending ratio of (1) component and (2) component may be such that the two perovskite compounds are mixed in accordance with (2) to the extent that two luminous peaks can be displayed, and (1 ) And (2) the types of the components and the like are appropriately determined.

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 1,000 or less, 0.005 or more and 100 or less, or 0.01 or more and 1 or less. .

It is preferable that the range of the blending ratio between the component (1) and the component (2) is the composition within the above range. Mixing two kinds of perovskite compounds depending on the component (2) can show two emission peaks.

In the composition of this embodiment, the total blending ratio of (1) component, (3) component, and (4) component may be compounded as long as the luminous effect due to (1) component can be exhibited well. The types of (1) component, (3) component, (4) component and the like are appropriately determined.

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

A composition in which the total blending ratio of the component (1), the component (3), and the component (4) is within the above-mentioned range is preferable. Since the aggregation of the component (1) is difficult to occur, the luminescence can be exhibited well.

A composition containing (1) component, (2) component and (5) component and at least one selected from the group consisting of (3) component and (4) component, or (1) component, (2) Component, (4 ') component, and (5) component, with respect to the total mass of the composition, an embodiment in which the total ratio of (1) component, (2) component, and (4') component is 90% by mass or more In the composition, the blending ratio of (1) component and (5) component may be sufficient as long as it can exhibit the degree of luminescence effect caused by (1) component, and the components of (1) to (5) component can be blended. The type is appropriate.

In a composition containing (1) component, (2) component, (5) component and at least one selected from the group consisting of (3) component and (4) component, (1) component and ( 5) The molar ratio [(1) / (5)] of the component may be 0.0001 or more and 1,000 or less, or 0.01 or more and 100 or less.

It is preferable that the range of the total blending ratio of the component (1) and the component (5) is the composition within the above range. Since the aggregation of the component (1) is hard to occur, the luminescence can be exhibited well.

Regarding the total mass of the composition, the composition comprising (1) component, (2) component, (6) component and at least one selected from the group consisting of (3) component and (4) component, Or the composition of the embodiment containing (1) component, (2) component, and (4 ') component in a total content ratio of 90% by mass or more, the blending ratio of (1) component to (6) component is good as long as it is good The degree of the luminous effect caused by the component (1) may be sufficient, and it may be appropriately determined according to the types of the components (1) to (6).

A composition comprising an embodiment of (1) component, (2) component, (5) component, (6) component and at least one selected from the group consisting of (3) component and (4) component, (The molar ratio [Si / B] of the metal ion of the component B of the component (1) to the Si element of the component (6) may be 0.001 or more and 2,000 or less, or 0.01 or more and 500 or less.

It is preferable that the range of the total blending ratio of the component (1) and the component (6) is a composition within the above-mentioned range. Since aggregation of the component (1) is difficult to occur, the luminescence can be exhibited well.

One aspect of the present invention is a composition comprising the component (1), the component (2), and the component (3), wherein the component (1) is a perovskite compound represented by CsPbBr ₃ , and the component (2) Is selected from 4-vinylbenzylamine, 4-carboxystyrene, 2-acrylamido-2-methylpropanesulfonic acid, 3-[[2- (methacryloxy) ethyl] di The polymer of at least one addition polymerizable compound of the group consisting of methylammonium] propionate and methacrylic acid is the mass ratio of the component (1) to the component (2) [(1) / ( 2)] The composition (A) is 0.001 to 0.100.

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

Another aspect of the present invention is a composition containing the component (1), the component (2), and the component (4 '), wherein the component (1) is a perovskite compound represented by CsPbBr ₃ , and the component ( 2) The component is selected from the group consisting of 4-vinylbenzylamine, 4-carboxystyrene, 2-propenylamine-2-methylpropanesulfonic acid, and 3-[[2- (methacryloxy) ethyl A polymer of an addition polymerizable compound of at least one of the group consisting of dimethyl] dimethylammonium] propionate and methacrylic acid, which is the mass ratio of the component (1) to the component (2) [( 1) / (2)] is a composition (C) of 0.001 to 0.050.

In the composition (C), the component (2) is preferably 4-vinylbenzylamine.

Another aspect of the present invention is a composition containing the component (1), the component (2), the component (3), and the component (6), wherein the component (1) is perovskite represented by CsPbBr ₃ Mineral compound, the component (2) is selected from the group consisting of 4-vinylbenzylamine, 4-carboxystyrene, 2-propenylamine-2-methylpropanesulfonic acid, 3-[[2- (methacrylic acid) Methoxy) ethyl] dimethylammonium] propionate and methacrylic acid are at least one polymer of an addition polymerizable compound in the group consisting of the component (1) and the component (2) The mass ratio [(1) / (2)] is 0.001 to 0.030, and the molar ratio [Si / B] between the metal ion of the B component of the perovskite compound and the Si element of the (6) component is 25 to 125的 组合 物 (D)。 The composition (D).

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

Another aspect of the present invention is a composition containing the component (1), the component (2), the component (3), and the component (6), wherein the component (1) is CsPbBr _(3-y) The perovskite compound represented by I _y (0 <y <3), the component (2) is selected from the group consisting of 4-vinylbenzylamine, 4-carboxystyrene, and 2-acrylamido-2-methylpropane Polymer of at least one addition polymerizable compound in the group consisting of sulfonic acid, 3-[[2- (methacryloxy) ethyl] dimethylammonium] propionate, and methacrylic acid The mass ratio [(1) / (2)] of the aforementioned (1) component to the aforementioned (2) component is 0.001 to 0.060, between the metal ion of the B component of the perovskite compound and the Si element of the (6) component The composition (E) having a ratio [Si / B] of 3 to 60.

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

<Manufacturing method of composition>

Hereinafter, an embodiment is explained about the manufacturing method of the composition in this invention. The composition of the embodiment of the present invention can be produced by the method for producing the composition of the embodiment. The composition of the present invention is not limited to a manufacturer produced by the method for producing a composition of the following embodiment.

(1) Manufacturing method of perovskite compounds containing A, B, and X as constituents

Perovskite compounds are produced by referring to existing documents (Nano Lett. 2015, 15,3692-3696, ACSNano, 2015, 9,4533-4542) by the method of the first embodiment or the second embodiment described below.

(First embodiment of a method for producing a perovskite compound containing A, B, and X as constituent components)

For example, the production method of the perovskite compound of the present invention includes a step of dissolving the B component, the X component, and the A component in a solvent x to obtain a solution g, a solution g obtained, and a solvent for the perovskite compound. A manufacturing method of a step of mixing a solvent y having a lower solubility than the solvent x used in the step of obtaining the solution g. More specifically, the method may include a step of dissolving a compound containing the B component and the X component with the A component or the compound containing the A and the X component in the solvent x to obtain a solution g, and the obtained solution g and the relative calcium A manufacturing method of a step of mixing a solvent of a titanium ore compound with a solvent y having a lower solubility than the solvent x used in the step of obtaining the solution g.

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

Hereinafter, a manufacturing method is described, which includes a step of dissolving a compound containing the B component and the X component with the A component or the compound containing the A and the X component in a solvent x to obtain a solution g, and a step of dissolving the obtained solution g with respect to The step of mixing the solvent y of the perovskite compound with a solvent lower than 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.

As far as the perovskite compound can be stably dispersed, the aforementioned production method preferably includes a step of adding a capped ligand. The capped ligand is preferably added before the aforementioned mixing step. The capped ligand may also be added to the solution g in which the A, B, and X components have been dissolved, and may be added to the perovskite compound. The solvent y having a lower solubility than the solvent x used in the step of obtaining the solvent g may be added to both the solvent x and the solvent y.

The aforementioned manufacturing method is preferably a step of removing coarse particles by means of centrifugal separation, filtration, or the like after the aforementioned mixing step. The size of the coarse particles removed in the foregoing steps is preferably 10 μm or more, more preferably 1 μm or more, and even more preferably 500 nm or more.

The aforementioned step of mixing the solution g and the solvent y may be (I) a step of dropping the solution g in the solvent y, or (II) a step of dropping the solvent y in the solution g, but the component (1) is increased From the viewpoint of dispersibility, (I) is preferred.

From the viewpoint of improving the dispersibility of the component (1), it is preferable to perform stirring at the time of dropping.

Although the temperature of the step of mixing the solution g and the solvent y is not particularly limited, it is preferably in a range of -20 ° C to 40 ° C from the viewpoint of ensuring the ease of analysis (1). It is more preferably within a range of -5 ° C to 30 ° C.

Although two types of solvents x and y having different solubility with respect to a solvent of a perovskite compound used in the aforementioned production method are not particularly limited, examples thereof include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, tertiary butanol, 1-pentanol, 2-methyl-2-butanol, methoxypropanol, diacetone alcohol, cyclohexanol, 2-fluoroethanol, 2 Alcohols such as 2,2-trifluoroethanol, 2,2,3,3-tetrafluoro-1-propanol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol Glycol ethers such as monoethyl ether acetate, triethylene glycol dimethyl ether; N-methyl-2-pyrrolidone, N, N-dimethylformamide, acetamide, N, N-dimethylethyl Organic solvents with amidine groups such as amidine; esters such as methyl formate, ethyl formate, propyl formate, amyl formate, methyl acetate, ethyl acetate, amyl acetate; γ-butyrolactone, acetone, diacetate Ketones such as methyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methyl cyclohexanone; diethyl ether, methyl-third butyl ether, diisopropyl ether, dimethoxy Methane, dimethoxyethane, 1,4-dioxane, 1,3-dioxolane, 4-methyldioxane Ethers such as pentane, tetrahydrofuran, methyltetrahydrofuran, anisole, and phenyl ether; organic solvents with nitrile groups such as acetonitrile, isobutyronitrile, propionitrile, and methoxyacetonitrile; etc. Organic solvents with carbonate groups; Organic solvents with halogenated hydrocarbon groups such as methylene chloride and chloroform; Organic solvents with hydrocarbon groups such as n-heptane, cyclohexane, n-hexane, benzene, toluene, and xylene; Two solvents selected from the group consisting of Chiazone.

The solvent x used in the step of obtaining the solution g in the aforementioned manufacturing method is preferably a solvent having a high solubility with respect to the solvent of the perovskite compound. For example, the aforementioned step is performed at room temperature (10 ° C or higher and 30 ° C or lower). Examples include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, tertiary butanol, 1-pentanol, 2-methyl-2-butanol, and methyl alcohol. Alcohols such as oxypropanol, diacetone alcohol, cyclohexanol, 2-fluoroethanol, 2,2,2-trifluoroethanol, 2,2,3,3-tetrafluoro-1-propanol; ethylene glycol mono Glycol ethers such as methyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, and triethylene glycol dimethyl ether; N-methyl-2-pyrrolidone, N, N- Dimethylformamide, acetamide, N, N-dimethylacetamide, and other organic solvents having an amine group; dimethylsulfine.

The solvent y used in the mixing step included in the aforementioned manufacturing method is preferably a solvent having a low solubility with respect to the solvent of the perovskite compound. For example, when the aforementioned step is performed at room temperature (10 ° C or higher and 30 ° C or lower), Examples include methyl formate, ethyl formate, propyl formate, pentyl formate, methyl acetate, ethyl acetate, and pentyl acetate; γ-butyrolactone, acetone, dimethyl ketone, and diisobutyl ketone , Ketones such as cyclopentanone, cyclohexanone, methylcyclohexanone; diethyl ether, methyl-third butyl ether, diisopropyl ether, dimethoxymethane, dimethoxyethane, Ethers such as 1,4-dioxane, 1,3-dioxolane, 4-methyldioxolane, tetrahydrofuran, methyltetrahydrofuran, anisole, phenyl ether, etc .; acetonitrile, isobutyronitrile , Propionitrile, methoxyacetonitrile and other organic solvents with nitrile groups; organic solvents with carbonate groups, such as ethyl carbonate, propylene carbonate; organic solvents with halogenated hydrocarbon groups, such as dichloromethane, chloroform; n- Organic solvents having a hydrocarbon group, such as pentane, cyclohexane, n-hexane, benzene, toluene, and xylene.

Among the two solvents having different solubility, the difference in solubility is preferably (100 μg / solvent 100 g) or more (90 g / solvent 100 g) or less, and more preferably (1 mg / solvent 100 g) or more (90 g / solvent 100 g) or less. From the viewpoint of setting the difference in solubility to (100 μg / solvent 100 g) or more (90 g / solvent 100 g) or less, for example, when the mixing step is performed at room temperature (10 ° C or higher and 30 ° C or lower), the step of obtaining a solution is performed. The solvent x to be used is an organic solvent having an amine group such as N, N-dimethylacetamidine or dimethylsulfinium, and the solvent y used in the mixing step is an organic group having a halogenated hydrocarbon group such as dichloromethane or chloroform. Solvent; organic solvents having a hydrocarbon group such as n-pentane, cyclohexane, n-hexane, benzene, toluene, xylene, etc. are preferred.

The method of extracting the perovskite compound from the obtained dispersion liquid containing the perovskite compound includes a method of performing solid-liquid separation and recovering only the perovskite compound.

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

(Second embodiment of the method for producing a perovskite compound containing A, B, and X as constituent components)

The production method of the perovskite compound may be a production method including a step of adding the component B, the X component, and the A component to a high-temperature solvent z to dissolve the solution h, and a step of cooling the obtained solution h. More specifically, the method includes a step of adding a compound containing the B component and the X component and a compound containing the A component or a compound containing the A component and the X component to a high-temperature solvent z to dissolve it to obtain a solution h, and Manufacturing method of the cooling step of the solution h.

The step of adding a compound containing the B component and the X component, and a component A or the compound containing the A and the X component to a high-temperature solvent z to dissolve to obtain a solution h is a step of adding the compound containing the B component and the X component, and A step of obtaining a solution h by adding component A or a compound containing component A and component X to the solvent z, and then raising the temperature.

In the aforementioned manufacturing method, the perovskite compound of the present invention can be precipitated by the difference in solubility caused by the temperature difference, and the perovskite compound of the present invention can be produced.

From the viewpoint that the perovskite compound can be stably dispersed, the aforementioned production method preferably includes a step of adding a blocked ligand. The end-capping ligand is preferably contained in the solution h before the aforementioned cooling step.

The aforementioned manufacturing method is preferably a step of removing coarse particles by means of centrifugal separation, filtration, etc. after including the aforementioned cooling step. The size of the coarse particles removed in the foregoing steps is preferably 10 μm or more, more preferably 1 μm or more, and even more preferably 500 nm.

Here, the high-temperature solvent z may be a solvent capable of dissolving the temperature of the compound containing the B component and the X component, and the component A or the compound containing the A and the X component. For example, a solvent of 60 ° C. to 600 ° C. is It is better to use a solvent of 80 ° C to 400 ° C.

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

The cooling rate is preferably 0.1 to 1,500 ° C / minute, and more preferably 10 to 150 ° C / minute.

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

The method of extracting the perovskite compound from the obtained dispersion liquid containing the perovskite compound includes a method of performing solid-liquid separation and recovering only the perovskite compound.

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

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

The manufacturing method of the composition containing (1) component, (2) component, and (3) component may be the following manufacturing method (a1), or the following manufacturing method (a2), for example.

Production method (a1): A method for producing a composition including a step of mixing the components (1) and (3) and a step of mixing the mixture of the components (1) and (3) with the component (2).

Production method (a2): A method for producing a composition including a step of mixing the components (1) and (2), and a step of mixing the mixture of the components (1) and (2) with the component (3).

In the aforementioned manufacturing method (a1), the component (1) is preferably dispersed in the component (3). The manufacturing method (a1) may be a method for manufacturing a composition including, for example, a step of dispersing the component (1) in the component (3) to obtain a dispersion, and a step of mixing the dispersion and the component (2).

In the embodiment, when producing a composition containing a polymer of an addition polymerizable compound having an ionic group, it can be set to the following production method (a3) or production method (a4).

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

Production method (a4): including a step of mixing (1) component and (2 ') component, a step of mixing a mixture of (1) component and (2') component with (3) component, and containing (1) A method for producing a composition in which a step of polymerizing a mixture of the component, the (2 ') component, and the (3) component is applied.

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

The mixing step included in the above-mentioned production method is preferably performed by stirring from the viewpoint of improving dispersibility.

Although the temperature in the mixing step included in the above-mentioned manufacturing method is not particularly limited, from the viewpoint of uniform mixing, it is preferably in a range of 0 ° C to 100 ° C, and in a range of 10 ° C to 80 ° C. The following ranges are better.

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

Method for applying polymerization treatment

The method of applying a polymerization treatment to 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 group contained in the addition polymerizable compound having an ionic group. limits. Examples of the method for applying the polymerization treatment include known methods such as a method of reacting with a polymerization initiator.

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

‧Photopolymerization initiator

Examples of the photopolymerization initiator include users generally in this technical field such as an ultraviolet type and a visible light type.

‧Photo radical polymerization initiator

The photo-radical polymerization initiator is a polymerization initiator that generates radicals upon receiving light such as ultraviolet rays and visible light. Examples of the photo-polymerization initiator include acetophenone and 2,2-dimethoxy-2- Phenylacetophenone, 2,2-diethoxyacetophenone, 4-isopropyl-2-hydroxy-2-methylphenylacetone, 2-hydroxy-2-methylphenylacetone, 4,4 ' -Bis (diethylamino) benzophenone, benzophenone, (o-benzyl) benzoic acid methyl ester, 1-phenyl-1,2-propanedione-2- (o- Ethoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (o-benzylidene) oxime, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, Carbonyl compounds such as benzoin isobutyl ether, benzoin octyl ether, diphenylethylene dione, benzyl dimethyl acetal, benzyl diethyl acetal, diethylfluorenyl, methylanthraquinone, chloroanthracene Anthraquinones or thiofluorenone derivatives such as quinone, chlorothalidone, 2-methylthiofluorenone, and 2-isopropylthiofluorenone; sulfur such as diphenyl disulfide and dithiocarbamate Compound.

‧Photocationic polymerization initiator

The cationic polymerization initiator can be used without particular limitation as long as it generates an acid by irradiating a known active energy ray, and examples thereof include sulfonium salts, iodonium salts, phosphonium salts, and pyridinium salts.

Examples include triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, bis (4- (diphenylsulfonyl) -phenyl) sulfide-bis (hexafluorophosphate) , Bis (4- (diphenylsulfonyl) -phenyl) sulfide-bis (hexafluoroantimonate), 4-bis (p-tolyl) sulfonyl-4'-third butylbenzene Carbonylcarbonyl-diphenylsulfide hexafluoroantimonate, 7-bis (p-tolyl) sulfonyl-2-isopropylthiofluorenone hexafluorophosphate, 7-bis (p-tolyl) sulfur Onium-2-isopropylthiofluorenone hexafluoroantimonate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, bis (dodecylphenyl) iodonium (Pentafluorophenyl) borate, tetrafluorophosphonium hexafluorophosphate, tetrafluorophosphonium hexafluoroantimonate.

‧ Thermal radical polymerization initiator

Thermal radical polymerization initiators are polymerization initiators which generate radicals upon heating, and examples thereof include 2,2'-azobisisobutyronitrile, 2,2'-azobisisovaleronitrile, and 2,2 '-Azobis (2,4-dimethylvaleronitrile), 4,4'-Azobis (4-cyanovaleric acid), 1,1'-Azobis (cyclohexanecarbonitrile), Azo compounds such as 2,2'-azobis (2-methylpropane), 2,2'-azobis (2-methylpropane) 2 hydrochloride, methyl ethyl ketone peroxide, Ketone peroxides such as methyl isobutyl ketone peroxide, cyclohexanone peroxide, and acetoacetone peroxide; isobutyl peroxide, benzamyl peroxide, and 2,4-bicyclobenzene Dimethyl peroxides such as formamyl peroxide, o-methylbenzyl peroxide, lauryl peroxide, p-chlorobenzyl peroxide, 2,4,4 -Hydrogen peroxides such as trimethylpentyl-2-hydrogen peroxide, dicumyl peroxide, cumene peroxide, third butyl peroxide, dicumyl peroxide, Dialkyl peroxides such as tributylcumene, di-tertiary butyl peroxide, ginseng (tertiary butyl peroxy) triazine, 1,1-di-tertiary butyl Peroxyketals such as peroxycyclohexane, 2,2-bis (third butylperoxy) butane, third butyl pivalate, third butyl peroxy-2-ethyl Hexanoate, third butyl peroxy isobutyrate, di-third butyl peroxy hexahydroterephthalate, di-third butyl peroxy hexahydrononanoate, Tert-butylperoxy-3,5,5-trimethylhexanoate, tert-butylperoxyacetate, tert-butylperoxybenzoate, tert-butyl Alkyl peresters such as peroxy trimethyl adipate, diisopropyl peroxy dicarbonate, di-second butyl peroxy dicarbonate, third butyl peroxy isopropyl Percarbonates such as alkyl carbonate may be 2,2'-azobisisobutyronitrile.

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

These polymerization initiators can be appropriately selected and used in accordance with the type and ratio of the addition polymerizable compound having an ionic group to be used.

For the total mass of the addition polymerizable compound having an ionic group contained in the composition, the amount of the polymerization initiator used is preferably 0.001 to 90% by mass, and more preferably 0.1 to 80% by mass, and It is more preferably 1 to 60% by mass.

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

‧Photopolymerization

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

There is no particular type of light to be irradiated as long as free radicals or ions can be generated by the photopolymerization initiator. Examples include visible light, ultraviolet rays, and near infrared rays. Examples of lamps used to generate such light include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, xenon lamps, ultraviolet LEDs, blue LEDs, white LEDs, H lamps manufactured by Fusion Corporation, D lamp, V lamp, carbon arc, tungsten lamp, fluorescent lamp, helium cadmium laser (or laser), argon laser, Nd: YAG laser, carbon dioxide laser, titanium sapphire laser, excimer laser, etc. Sunlight can also be used.

The irradiation time and irradiation intensity can be appropriately set 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 of the photopolymerization treatment may be any temperature sufficient for polymerization. For example, the temperature is preferably 5 ° C to 150 ° C, more preferably 10 ° C to 100 ° C, and even more preferably 15 ° C to 80 ° C.

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

Although there are no particular restrictions on the ambient gas in the photopolymerization process, in order to improve the reactivity, it is preferable to replace it with an inert gas such as nitrogen or argon.

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

‧Thermal polymerization

For the thermal polymerization reaction, it is preferable to heat the composition containing an addition polymerizable compound having an ionic group and a thermal polymerization initiator, and heat it at an appropriate temperature to generate radicals or ions from the thermal polymerization initiator. .

The temperature of the polymerization treatment may be any temperature sufficient for polymerization. For example, it is preferably 5 ° C to 200 ° C, more preferably 10 ° C to 150 ° C, and even more preferably 15 ° C to 100 ° C.

The time required for the polymerization treatment may be any time sufficient for the polymerization to take place, and examples include 1 minute to 1 week, more preferably 10 minutes to 5 days, and more preferably 30 minutes to 3 days.

Although there are no particular restrictions on the surrounding ambient gas for the polymerization treatment, in order to improve the reactivity, it is preferable to replace it with an inert gas such as nitrogen or argon.

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

In this embodiment, the component (2) and the component (3) may be mixed by any step included in the method for producing the component (1). For example, the following manufacturing method (a5) or the following manufacturing method (a6) may be used.

Production method (a5): including a step of dissolving a compound containing the B component and the X component, a component A or a compound containing the A and X components with the component (2) in the component (3) to obtain a solution g, and The manufacturing method of the process of mixing the obtained solution g and the solvent with respect to the perovskite compound in a solvent y lower than the solvent (y) used in the step of obtaining the solution.

Production method (a6): A solution containing a component B and an X component, a component A or a compound containing the A and X components, and the component (2) added to the component (3) at a high temperature and dissolved to obtain a solution h And a manufacturing method of a step of cooling the obtained solution h.

In the present embodiment, when producing a composition containing a polymer of an addition polymerizable compound having an ionic group, it can be set to the following production method (a7) or the following production method (a8).

Production method (a7): including a step of dissolving a compound containing the B component and the X component, a component A or a compound containing the A and the X component and the (2 ') component in the (3) component to obtain a solution g, and The step of mixing the solution g with the solvent relative to the perovskite compound at a lower solvent than the solvent (y) used in the step of obtaining the solution (y), and mixing it with (1), (2 '), and (3) A manufacturing method in which a mixture of ingredients is subjected to a polymerization process.

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

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

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

For example, a method for producing a composition containing (1) component, (2) component, (3) component, and (5) component, in addition to mixing in any one of the above-mentioned production methods (a1) to (a4) ( 5) Other than components, it can be set to the same method as the manufacturing method of the composition containing (1) component, (2) component, and (3) component.

In the present embodiment, from the viewpoint of improving the dispersibility of the component (1), it is included in the method for producing a perovskite compound in which the component (1) has A, B, and X as constituent components. It is preferable to mix the component (5) in either step. For example, it is preferable to manufacture by the following manufacturing method (b1), manufacturing method (b2), manufacturing method (b3), or manufacturing method (b4).

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

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

Production method (b3): Dissolving a compound containing component B and X component, component A or compound containing component A and X, component (2 ') and component (5) in component (3) to obtain solution g A step of mixing the obtained solution g with a solvent having a lower solubility in the solvent relative to the perovskite compound than the component (3) used in the step of obtaining the solution, and the step (1), (2 ') A manufacturing method in which the component, the component (3), and the mixture of the component (5) are subjected to a polymerization process.

Production method (b4): Adding a compound containing the B component and the X component, a component A or a compound containing the A and the X component, the (2 ′) component and the (5) component to a high temperature component (3), A step of dissolving to obtain a solution h, a step of cooling the obtained solution h, and a step of applying a polymerization treatment to the cooled solution h containing the components (1), (2 '), (3), and (5) Step manufacturing method.

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

Examples of a method for producing a composition containing (1) component, (2) component, and (4) component include a method of mixing (1) component, (2) component, and (4) component.

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

In the step of mixing the components (1), (2), and (4), although the temperature is not particularly limited, from the viewpoint of uniform mixing, it is preferably in a range of 0 ° C to 100 ° C. A more preferable range is 10 ° C to 80 ° C.

Examples of the method for producing the composition containing the component (1), the component (2), and the component (4) include the following production methods (c1), (c2), and (c3).

Production method (c1): A production method including a step of dispersing the component (1) in the component (4) to obtain a dispersion, and a step of mixing the obtained dispersion with the component (2).

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

Production method (c3): A production method including a step of dispersing a mixture of the component (1) and the component (2) in the component (4).

Among the production methods of (c1) to (c3), the production method of (c1) is preferred in terms of improving the dispersibility of the component (1). According to the aforementioned method, a dispersion of the component (1) in the component (4) and a mixture of the component (2) can be obtained as a composition of the present invention.

In the step of obtaining each dispersion in the manufacturing method of (c1) to (c3), the component (4) may be dropped into either or both of the components (1) and (2), or Either or both of the component (1) and the component (2) are dripped into the component (4).

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

Each of the mixing steps included in the production method of (c1) to (c3), the component (1) or (2) may be dropped into the dispersion, or the dispersion may be dropped into the (1) or (2) component .

From the viewpoint of improving dispersibility, it is preferable to drop the component (1) and the component (2) into the dispersion.

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

The solvent for dissolving the polymer is not particularly limited as long as it is a solvent capable of dissolving the polymer (resin), but it is preferable to dissolve the component (1) used in the present invention.

As the solvent for dissolving the polymer, for example, the solvent described as the component (3) can be used.

Meanwhile, the method for producing a composition containing the component (1), the component (2), and the component (4) may be the following production method (c4) or production method (c5).

Production method (c4): a step of dispersing the component (1) in the component (3) to obtain a dispersion liquid, mixing the obtained dispersion liquid with the component (4) to obtain a mixed liquid step, and mixing the obtained mixed liquid with ( 2) A method for producing a composition in the step of mixing ingredients.

Production method (c5): a step of dispersing the component (1) in the component (3) to obtain a dispersion liquid, mixing the dispersion liquid and the component (2 ′) to obtain a mixed liquid step, and applying a polymerization treatment to the mixed liquid, A process for obtaining a mixed solution of a polymer containing an addition polymerizable compound having an ionic group, and a method for producing the composition of the step of mixing the mixed solution containing the polymer with the component (4).

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

The method for producing a composition containing (1) component, (2) component, (4) component, and (5) component, in addition to adding (5) component, can be set as described with (1) component, (2) ) And the method for producing the composition of the component (4) are the same.

(5) The component may be added to any one of the steps of the above-mentioned method for producing a perovskite compound containing A, B, and X as constituent components in (1), or may include the component (1), (2) The component and (4) are added in any one of the steps of the method for producing the composition of the component.

(5) The component refers to any step included in the method for producing a perovskite compound containing A, B, and X as the constituent component of the component (1) from the viewpoint of improving the dispersibility of the component (1). It is better to add.

In the method for producing a composition containing (1) component, (2) component, (4) component, and (5) component, even if the component (3) solvent is used, it can be set to, for example, at least a part of (5) A component-coated (1) component is dispersed in (3) component, a dispersion in which (2) component is dispersed in (3) component, a mixture with (4) component, or at least a part of (5) The component-coated (1) component and (2) component are dispersed in a dispersion of the component (3) and a mixture of the component (4) to obtain the composition of this embodiment.

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

The total content of (1), (2), and (4 ') components is 90% by mass or more based on the total mass of the composition containing (1), (2), and (4') components. Examples of the method for producing the composition include the following production method (Y).

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

As the mixing step included in the manufacturing method, a mixing method similar to the manufacturing method of the composition containing the components (1), (2), and (4) described above can be used.

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

Production method (d1): A production method including a step of dispersing component (1) in a polymerizable compound to obtain a dispersion, a step of mixing the obtained dispersion with (2), and a step of polymerizing a polymerizable compound.

Production method (d2): A production method including a step of dispersing the component (1) in a polymer dissolved in a solvent to obtain a dispersion, a step of mixing the obtained dispersion with the component (2), and a step of removing the solvent.

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

Production method (d4): A production method including a step of dispersing the component (2) in a polymer dissolved in a solvent to obtain a dispersion, a step of mixing the obtained dispersion with the component (1), and a step of removing the solvent.

Production method (d5): A production method including a step of dispersing a mixture of the components (1) and (2) in a polymerizable compound, and a step of polymerizing the polymerizable compound.

Production method (d6): A production method including a step of dispersing a mixture of the component (1) and the component (2) in a solvent, and removing the solvent.

The step of removing the solvent included in the aforementioned manufacturing method may be a step of leaving it to stand at room temperature to naturally dry it, or a step of drying under reduced pressure using a vacuum dryer or evaporating the solvent by heating.

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

The step of polymerizing a polymerizable compound in the aforementioned production method may be carried out by using a known polymerization reaction such as radical polymerization as appropriate.

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

Although the radical polymerization initiator is not particularly limited, examples thereof include a photo radical polymerization initiator and the like.

Examples of the photoradical polymerization initiator include bis (2,4,6-trimethylbenzyl) -phenylphosphine oxide and the like.

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

Relative to the total mass of a composition containing (1) component, (2) component, (4 ') component, and (5) component, (1) component, (2) component, (4') component, and (5) component A method for producing a composition having a total content ratio of 90% by mass or more, except for, for example, the total mass of the composition containing (1) component, (2) component, and (4 ') component, (1) component, (2 ) And (4 ') components, the total content of which is 90% by mass or more. In addition to the step (5) added to any of the steps included in the method for producing a composition, the available and explained components (1), (2) The same method as the manufacturing method of the composition of the total mass of the component and the component of (4 ') component, and the total content ratio of (1) component, (2) component, and (4') component is 90 mass% or more.

From the viewpoint of improving the dispersibility of the perovskite compound, the component (5) is any one of the following steps included in the method for producing a perovskite compound containing (1) A, B, and X as constituent components. It is better to add in.

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

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

‧ The step of mixing (1) and (2) above with a polymer dissolved in a solvent.

[Manufacturing method of composition containing (6) component]

The manufacturing method of the composition containing a component (6) can be set to the same method as the manufacturing method of the said composition except having mixed the component (6). Before mixing (1) and (2), it is preferable to mix (1) and (6), for example, the following manufacturing method (a1-1) or the following manufacturing method (a2- 1).

Production method (a1-1): including a step of mixing (1) component and (3) component, a step of mixing a mixture of (1) component and (3) component with (6) component, and containing (1) A method for producing a composition in the step of mixing the component, the component (3), and the mixture of the component (6) and the component (2).

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

[Steps of mixing with (1) -1 ingredients]

The manufacturing method of the composition of this embodiment mentioned above may further have the process of mixing the said (1) -1 component. In this step, a dispersion liquid containing a perovskite compound and a solvent having a different emission peak wavelength from the component (1) can be prepared, and the dispersion liquid and the components (1) and (2) can be used as necessary components and other optional components can be included. The component mixture is mixed and implemented. In this step, the component (1) -1 may be a mixed liquid containing the component (1) -1 and the optional component containing the component (2) and the other optional components described above. The mixed liquid containing the component (1) -1 and the optional component and the component (2) and the other optional components mentioned above can be used as described in the components (1) and (2) as necessary components, and contains other optional components. The mixed solution was produced in the same manner.

的 Determination of perovskite compounds≫

The amount of the perovskite compound contained in the composition of the present invention is an Inductively Coupled Plasma Mass Spectrometer (ICP-MS) (e.g., Perkin Elmer) (Manufactured by ELAN DRCII) and ion chromatography (for example, manufactured by Thermo Fisher Scientific, Integrion).

The measurement is performed after dissolving the perovskite compound using a good solvent such as N, N-dimethylformamide.

的 Determination of luminescence spectrum≫

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

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

In the composition containing the component (1), the component (2), and the component (4), the mixing ratio of the system in which the concentration of the perovskite compound contained in the composition is adjusted to 2,000 ppm (μg / g) is measured. Luminescence spectrum. The same applies when the component (4) is replaced with the component (4 ').

评估 Evaluation of Luminescence Peaks When Two Perovskite Compounds Are Mixed 1≫

In 1 mL of the dispersion composition of the present invention containing a perovskite compound (perovskite compound 1), a perovskite compound (perovskite compound 2) having a different emission peak wavelength from the perovskite compound is mixed. Measure the luminescence spectrum before and after mixing the two perovskite compounds, and use it as the evaluation index of the luminescence spectrum to calculate (the emission peak wavelength (nm) of the perovskite compound 1 before the mixing)-(the perovskite compound 1 after the mixing Absolute value of luminescence peak wavelength (nm)), and (Luminescence peak wavelength (nm) of perovskite compound 2 before mixing)-Absolute value of (luminescence peak wavelength (nm) of perovskite compound 2 after mixing) , And the number of peaks.

评估 Evaluation of Luminescence Peaks When Two Perovskite Compounds Are Mixed 2≫

A perovskite compound (perovskite compound 1) containing a perovskite compound (perovskite compound 1) is mixed with a perovskite compound (perovskite compound 2) having a light emission peak wavelength different from the perovskite compound to form a film, and then cut. The thickness is 100 μm and 1 cm × 1 cm. Measure the luminescence spectrum before and after mixing the two perovskite compounds, and use it as the evaluation index of the luminescence spectrum to calculate (the emission peak wavelength (nm) of the perovskite compound 1 before the mixing)-(the perovskite compound 1 after the mixing Absolute value of luminescence peak wavelength (nm)), and (Luminescence peak wavelength (nm) of perovskite compound 2 before mixing)-Absolute value of (luminescence peak wavelength (nm) of perovskite compound 2 after mixing) , And the number of peaks.

The composition of the embodiment may be evaluated for the emission peaks of the two perovskite compounds measured by the above-mentioned measurement method when they are mixed, and may be 23 nm or less, 20 nm or less, or 15 nm or less, and the number of peaks may be Two.

In one aspect of the present invention, the light emission peaks of the two perovskite compounds measured by the above-mentioned measurement method when mixed are preferably 0 nm to 23 nm, more preferably 0 nm to 20 nm, and more preferably 0 nm. Above 15nm is more preferable.

Although there are no particular restrictions on the emission peaks of the two types of perovskite compounds measured by the above-mentioned measurement method, for example, the two emission peak wavelengths that can be confirmed are preferably the absolute value of the difference between the wavelengths is 30 nm or more. It is more preferably 50 nm or more, and more preferably 100 nm or more. At the same time, the minimum luminous intensity in the wavelength region between the two luminous peaks is preferably less than 80% of the luminous intensity of the higher luminous peak among the two luminous peak wavelengths, more preferably 50% or less, and 30 % Is even better.

<Film>

The film of the present invention is a film using a composition containing (1) component, (2) component, and (4 ') component, and is (1) component, (2) component, and (4') with respect to the total mass of the composition ) A film of a composition containing a total content of 90% by mass or more of the components. The said composition may contain (5) component.

The shape of the film is not particularly limited, and may be any shape such as a sheet shape or a rod shape. In this specification, "rod-shaped shape" means the shape which has an anisotropy, for example. Examples of the shape having an anisotropy include a plate-like shape having different lengths of the sides.

The thickness of the film may be from 0.01 μm to 1,000 mm, from 0.1 μm to 10 mm, or from 1 μm to 1 mm. In the present specification, the thickness of the aforementioned film can be measured at any three places with a micrometer, and the average value is obtained by calculating the average value.

The film may be a single layer or a multilayer. In the case of a plurality of layers, the composition of the embodiment of the same kind may be used for each layer, or the composition of the embodiments of different kinds may be used for each layer.

The film can be formed on a substrate by, for example, a manufacturing method (i) to (iV) of a laminated structure to be described later. At the same time, the film can be peeled from the substrate.

<Laminated Structure>

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

Among the plural layers included in the laminated structure, any layer other than the above-mentioned film may be any layer such as a substrate, a barrier layer, and a light scattering layer.

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

(Substrate)

The layer which the laminated structure of this invention can have is not specifically limited, A board | substrate is mentioned.

The substrate is not particularly limited, and may be a film. In terms of extracting the light that emits light, it is preferable to use a transparent one. As the substrate, for example, a polymer such as polyethylene terephthalate or a known substrate such as glass can be used.

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

FIG. 1 is a cross-sectional view schematically showing the configuration of a laminated structure according to this embodiment. The first laminated structure 1 a is such that the film 10 of this embodiment is provided between the first substrate 20 and the second substrate 21. The film 10 is sealed with a sealing layer 22.

Another aspect of the present invention is a laminated structure 1a, which includes a first substrate 20, a second substrate 21, and a film 10 and a sealing layer 22 of this embodiment located between the first substrate 20 and the second substrate 21. In the multilayer structure, the sealing layer is disposed on a surface not connected to the first substrate 20 and the second substrate 21 of the film 10.

(Barrier layer)

The layer which the laminated structure of this invention can have is not specifically limited, A barrier layer is mentioned. A barrier layer may be contained from the viewpoint of protecting the aforementioned composition from outside water vapor and air in the atmosphere.

The barrier layer is not particularly limited, and in terms of extracting light, a transparent barrier layer is preferred. As the barrier layer, a known barrier layer such as a polymer such as polyethylene terephthalate or a glass film can be used.

(Light scattering layer)

The layer which the laminated structure of this invention can have is not specifically limited, A light-scattering layer is mentioned. A light-scattering layer may be contained in order to make effective use of incident light.

The light-scattering layer is not particularly limited, and in terms of extracting luminous light, a transparent one is preferred. As the light-scattering layer, a light-scattering particle such as silicon dioxide particles or a known light-scattering layer such as an enlarged diffusion film can be used.

<Light-emitting device>

The light-emitting device of the present invention can be obtained by combining the composition or the laminated structure of the embodiment of the present invention with a light source. A light-emitting device is a device that irradiates light emitted from a light source onto a composition or a multilayer structure provided at a subsequent stage to cause the composition or the multilayer structure to emit light and extract light. Among the plurality of layers included in the laminated structure in the light-emitting device, the layers other than the above-mentioned film, substrate, barrier layer, and light scattering layer include a light reflecting member, a brightness enhancement portion, a cymbal, a light guide plate, Any layer such as a dielectric material layer between elements.

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

(Light source)

Although the light source constituting the light-emitting device of the present invention is not particularly limited, a light source having an emission wavelength of 600 nm or less is preferred from the viewpoint of emitting the component (1) in the composition or the laminated structure. The light source may be a known light source such as a light emitting diode (LED) such as a blue light emitting diode, a laser, or an EL.

(Light reflecting member)

Although the layer which the laminated structure which comprises the light emitting device of this invention may have is not specifically limited, A light reflection member is mentioned. From the viewpoint of irradiating the light from the light source to the aforementioned composition or the laminated structure, a light reflecting member may be contained. The light reflecting member is not particularly limited, but may be a reflecting film.

As the reflective film, a known reflective film such as a mirror, a film of reflective particles, a reflective metal film, or a reflector can be used.

(Brightness Enhancement Section)

Although the layer which the laminated structure which comprises the light emitting device of this invention may have is not specifically limited, A brightness enhancement part is mentioned. In order to reflect a part of the light and return it in the direction of light transmission, a brightness enhancement portion may be included.

(Cymbal)

The layer which the laminated structure which comprises the light emitting device of this invention may have is not specifically limited, A cymbal is mentioned. The cymbal sheet typically has a base portion and a crotch portion. In addition, the base material portion can be omitted in accordance with the adjacent material. The septum can be adhered to the adjacent component through any suitable adhesive layer (eg, adhesive layer, adhesive layer). The cymbal is formed by juxtaposing a plurality of convex cells on the side opposite to the viewing side (back side). By arranging the convex portion of the cymbal toward the back side, the light transmitted through the cymbal can be easily collected. At the same time, as long as the convex portion of the cymbal is disposed toward the back side, a display with high brightness can be obtained with less reflected light that does not enter the cymbal compared with the case where the convex portion is disposed toward the viewing side.

(Light guide plate)

Although the layer which the laminated structure which comprises the light emitting device of this invention may have is not specifically limited, A light guide plate is mentioned. As the light guide plate, for example, a light guide plate that can form a lens pattern on the back side, such as a light guide plate that can deflect light from the horizontal direction to the thickness direction, and a 稜鏡 shape on the back side and / or the viewing side, etc. Any suitable light guide.

(Dielectric material layer between components)

Although the layer that the laminated structure constituting the light-emitting device of the present invention may have is not particularly limited, a layer made of one or more dielectric materials on the optical path between adjacent elements (layers) (inter-element Dielectric material layer).

Although there is no particular limitation on one or more of the dielectric material layers contained in the element, vacuum, air, gas, optical materials, adhesives, optical adhesives, glass, polymers, solids, liquids, Gels, hardened materials, optical bonding materials, refractive index integrated or non-index integrated materials, refractive index gradient materials, cladding or anti-cladding materials, spacers, silicone, brightness enhancement materials, scattering or diffusion materials, reflection or anti- Reflective materials, wavelength selective materials, wavelength selective anti-reflection materials, color filters, or suitable media known in the foregoing technical field.

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

Specifically, (E1) the composition of the present invention is placed in a glass tube and sealed, and this is arranged along one side (side surface) of the light guide plate between a blue light emitting diode as a light source and the light guide plate. A backlight (on-edge backlight) that converts blue light into green light or red light.

At the same time, (E2) the composition of the present invention may be sheeted, and a film sealed by sandwiching the sheet with two barrier films is provided above the light guide plate, and the light guide plate is provided on one side (side surface) The blue light emitting diode) is irradiated with the blue light on the sheet through the light guide plate, and is converted into a green light or a red light backlight (surface-mounted backlight).

In the meantime, (E3) a backlight (a crystal-based backlight (on) in which the composition of the present invention is dispersed in a resin or the like, is disposed near a blue light-emitting body, and converts irradiated blue light into green light or red light -chip backlight)).

In addition, (E4) A backlight in which the composition of the present invention is dispersed in a resist, is provided on a color filter, and converts blue light irradiated by a light source into green light or red light.

In the meantime, specific examples of the light-emitting device of the present invention include molding the composition of the embodiment of the present invention and arranging it behind the blue light-emitting diode as a light source, and converting blue light into green light or red light. Lighting that emits white light.

<Display>

As shown in FIG. 2, the display 3 of this embodiment includes a liquid crystal panel 40 and the aforementioned light-emitting device 2 in this order from the viewing side. The light-emitting device 2 includes a second laminated structure 1 b and a light source 30. The second laminated structure 1 b is the one in which the aforementioned first laminated structure 1 a further includes a cymbal 50 and a light guide plate 60. Display and can be equipped with any other suitable material.

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

(LCD panel)

The liquid crystal panel typically includes a liquid crystal cell (also referred to as 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 can arrange the respective absorption axes as if they are substantially vertical or parallel.

(LCD cell)

The liquid crystal cell system includes a pair of substrates and a liquid crystal layer as a display medium held between the substrates. In a general configuration, a color filter and a black matrix are provided on one substrate, and the other substrate is provided with a switching element that regulates the electro-optical characteristics of the liquid crystal, a scanning line that provides a gate signal to the switching element, and provides The signal line of the source signal, the pixel electrode and the counter electrode. The substrate gap (cell gap) can be adjusted with a spacer or the like. The side connected to the liquid crystal layer of the substrate may be provided with, for example, an alignment film made of polyfluorene.

(Polarizer)

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

As the polarizer, any suitable polarizer can be used. Examples include hydrophilic polymer films such as polyvinyl alcohol-based films, partial methylalized polyvinyl alcohol-based films, and ethylene-vinyl acetate copolymer polymer-based saponified films, and have adsorbed iodine or dichroic dyes. Polyaxially oriented films such as uniaxially stretched dichroic materials, dehydrated products of polyvinyl alcohol, or dehydrochlorinated products of polyvinyl chloride. Among them, a uniaxially stretched polarizer is particularly preferred after the polyvinyl alcohol-based film adsorbs iodine or a dichroic substance, because of its high polarization dichroism ratio.

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

<LED>

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

The LED containing the composition of the present invention includes, for example, a structure in which the composition of the present invention is mixed with conductive particles such as ZnS and laminated to form a film. One area layer has an n-type transport layer and the other area layer has a p-type transport layer. In this case, the holes of the p-type semiconductor and the electrons of the n-type semiconductor emit light in such a manner that particles containing the component (1) and component (2) in the composition of 1 on the joint surface cancel the charge.

<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 structure of the solar cell is not particularly limited, and examples thereof include a fluorine-doped tin oxide (FTO) substrate, a titanium dioxide dense layer, a porous alumina layer, an active layer containing the composition of the present invention, 2, 2 Hole transporting layers such as', 7,7'-N (N, N'-di-p-methoxyphenylamine) -9,9'-spirobifluorene (spiro-MeOTAD) and silver (Ag) electrodes Of solar cells.

Titanium dioxide dense layer has the function of electron transport, the effect of preventing roughness of FTO, and the function of preventing reverse electron movement.

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

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

<Manufacturing method of laminated structure>

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

Manufacturing method (i): a manufacturing method of a laminated structure, comprising the steps of mixing (1) component, (2) component, (3) component, and (4 '), and applying the obtained mixture to a substrate, With solvent removal steps.

Manufacturing method (ii): A method for manufacturing a multilayer structure, comprising the steps of mixing (1) component, (2) component, and a polymer dissolved in a solvent, applying the resulting mixture to a substrate, and removing the solvent A step of.

Manufacturing method (iii): A manufacturing method of a multilayer structure, comprising a component (1), a component containing (1) component, (2) component, and (4 ') component with respect to the total mass of the composition, (2) A step of bonding a composition having a total content ratio of the component and (4 ′) component of 90% by mass or more to the substrate.

Production method (iv): A production method including a step of mixing the components (1), (2), and a polymerizable compound, a step of applying the obtained mixture to a substrate, and a step of polymerizing the polymerizable compound.

The mixing step, the step of removing the solvent, and the step of polymerizing the polymerizable compound included in the manufacturing method of (ii) may be the same as those described above containing the components (1), (2), and (4 '). The composition is the same as the steps included in the method for producing a composition having a total content ratio of (1) component, (2) component, and (4 ′) component to the total mass of the composition of 90% by mass or more.

The step of coating on a substrate included in the manufacturing methods of (i), (ii), and (iv) is not particularly limited, and a gravure coating method, a rod coating method, a printing method, a spray method, and a spin coating method can be used Well-known coating methods such as a method, a dip coating method, and a die coating method.

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

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

The method for manufacturing a laminated structure may further include a step of laminating any of the laminated structures obtained in (i) to (iv).

Any film that can be bonded includes, for example, a reflective film and a diffusion film.

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

The above-mentioned adhesive is not particularly limited as long as it is a compound that does not dissolve the components (1) and (2), and a known adhesive can be used.

<Manufacturing Method of Light-Emitting Device>

For example, the manufacturing method which includes the process of providing the said light source, and providing the said composition or laminated structure in the optical path from a light source to a subsequent stage is mentioned.

The technical scope of the present invention is not limited to those described in the above embodiments, and various changes can be added without departing from the gist of the present invention.

    [Example]    

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

(Determination of the concentration of perovskite compounds)

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.

N, N-dimethylformamide was added to a dispersion liquid containing a redispersed perovskite compound and a solvent to dissolve the perovskite compound.

Then, it measured using ICP-MS (made by Perkin Elmer, ELAN DRCII) and ion chromatography (made by Thermo Fisher 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 using an absolute PL quantum yield measurement device (made by Hamamatsu Photonics Co., Ltd., C9920-02) under excitation light at 450 nm, room temperature, and air.

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

To 1 mL of the dispersion compositions obtained in Examples 1 to 18 and Comparative Examples 1 to 3, different perovskite compounds were added, and they were prepared with n-hexane as if each had a concentration of 200 ppm (μg / g). The luminescence spectrum was measured before and after the mixing of the two kinds of perovskite compounds, and as an evaluation index of the luminescence spectrum, (the luminescence peak (nm) of the perovskite compound 1 before the mixing)-(the perovskite compound 1 after the mixing Absolute value of luminescence peak (nm)) and (luminescence peak (nm) of perovskite compound 2 before mixing)-absolute value of (luminescence peak (nm) of perovskite compound 2 after mixing), and peak number .

(Observed with a scanning electron microscope)

The compositions obtained in Examples 14 and 18 were observed with a scanning electron microscope (manufactured by Japan Electronics Co., Ltd., JEM-5500). The observation sample was obtained by fixing a naturally-dried powder at room temperature to a carbon double-sided adhesive tape for SEM, followed by gold evaporation. The sample was observed after the acceleration voltage was set to 20 kV.

The agglomerates are observed in the composition, and the average Fischer's diameter is set to the average of the fischer's diameters of 20 agglomerates.

观察 Observation of perovskite compounds with a transmission electron microscope≫

The perovskite compound was observed with a transmission electron microscope (JEM-2200FS, manufactured by Japan Electronics Corporation). The observation sample was obtained by taking a perovskite compound from a dispersion composition containing a perovskite compound in a grid with a supporting film, and then setting the acceleration voltage to 200 kV for observation.

The average Fisher's diameter is set to the average of the Fisher's diameter of 20 perovskite compounds.

(Synthesis of composition)

[Example 1]

0.814 g of cesium carbonate, 40 mL of a 1-octadecene solvent, and 2.5 mL of oleic acid were mixed. The mixture was stirred with a magnetic stirrer and heated at 150 ° C. for 1 hour while flowing nitrogen gas to prepare a cesium carbonate solution 1.

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

After the lead bromide dispersion was heated to a temperature of 160 ° C, 1 1.6 mL of the above-mentioned cesium carbonate solution was added. After the addition, the reaction vessel was immersed in ice water, and the temperature was lowered to room temperature to obtain a dispersion.

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

The concentration of perovskite compound 1 measured by ICP-MS and ion chromatography was 2,000 ppm (μg / g).

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

When the X-ray diffraction pattern of the compound recovered by naturally drying the solvent was measured with an X-ray diffraction measuring device (XRD, Cu Kα line, X'pert PRO MPD, manufactured by Spectroscopy Corporation), there was a position from 2θ = 14 ° ( The peak of hk1) = (001) was confirmed to have a three-dimensional perovskite crystal structure.

The average Fisher's diameter of the perovskite compound observed by TEM was 11 nm.

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

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

Next, the dispersion was centrifuged at 10,000 rpm for 5 minutes, and the precipitate was separated to obtain a precipitated perovskite compound 2. After dispersing the perovskite compound 2 in 5 mL of n-hexane, 100 μL of the dispersion was extracted and redispersed in 0.9 mL of n-hexane to obtain a dispersion 2 containing a perovskite compound 2 and a solvent.

The average Fisher's diameter of the perovskite compound observed by TEM was 19 nm.

The concentration of perovskite compound 2 measured by ICP-MS and ion chromatography was 2,000 ppm (μg / g).

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

After 3 µL of 4-vinylbenzylamine was mixed with the dispersion 1 containing the perovskite compound 1 and the solvent described above, 30 mg of 2,2'-azobisisobutyronitrile was mixed. After substitution with nitrogen, the mixture was polymerized while stirring at 60 ° C. with a stirrer for 4 hours to obtain a composition. In the composition, the mass ratio is a perovskite compound 1 / 4-vinylbenzylamine = 0.045.

After diluting the perovskite compound 2 with n-hexane to 200 ppm (μg / g), the peak wavelength of the emission spectrum measured by the quantum yield measuring device was 521 nm.

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

(Luminescence peak wavelength (nm) of perovskite compound 1 before mixing)-(Luminescence peak wavelength (nm) of perovskite compound 1 after mixing) The absolute value is 9nm and (Perovskite compound 2 before mixing The absolute value of the emission peak wavelength (nm))-(the emission peak wavelength (nm) of the perovskite compound 2 after mixing) is 16 nm.

[Example 2]

It was obtained in the same manner as in Example 1 except that 4-vinylbenzylamine was set to 10 μL and the mass ratio was set to [Perovskite Compound 1] / [4-vinylbenzylamine] = 0.013.组合 物。 Composition.

After diluting the perovskite compound 2 with n-hexane to 200 ppm (μg / g), the peak wavelength of the emission spectrum measured by the quantum yield measuring device was 522 nm.

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

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

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

[Example 3]

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

After diluting the perovskite compound 2 with n-hexane to 200 ppm (μg / g), the peak wavelength of the emission spectrum measured by the quantum yield measuring device was 522 nm.

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

(Luminescence peak wavelength (nm) of perovskite compound 1 before mixing)-(Luminescence peak wavelength (nm) of perovskite compound 1 after mixing) The absolute value is 19 nm, and (Perovskite compound before mixing The emission peak wavelength (nm) of 2)-(the emission peak wavelength (nm) of the perovskite compound 2 after mixing) has an absolute value of 4 nm.

[Example 4]

A composition was obtained in the same manner as in Example 3 except that 4-carboxystyrene was set to 30 mg and the mass ratio was set to [Perovskite Compound 1] / [4-carboxystyrene] = 0.0044.

After diluting the perovskite compound 2 with n-hexane to 200 ppm (μg / g), the peak wavelength of the emission spectrum measured by the quantum yield measuring device was 522 nm.

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

As shown in FIG. 3, when the composition mixed dispersion liquid 2 of Example 4 was used, the emission peak wavelength of the perovskite compound 1 and the emission peak wavelength of the perovskite compound 2 maintained a peak at 516 nm and a peak at 642 nm, respectively.

(Luminescence peak wavelength (nm) of perovskite compound 1 before mixing)-(Luminescence peak wavelength (nm) of perovskite compound 1 after mixing) The absolute value is 6 nm, and (Perovskite compound before mixing The emission peak wavelength (nm) of 2)-(the emission peak wavelength (nm) of the perovskite compound 2 after mixing) has an absolute value of 4 nm.

[Example 5]

10 mg of 2-acrylamido-2-methylpropanesulfonic acid was mixed with the dispersion liquid 1 containing the perovskite compound 1 and the solvent described in Example 1, and then 30 mg of 2,2'-azobisisobutyronitrile was mixed. After substitution with nitrogen, the composition was polymerized while being stirred at 60 ° C. with a stirrer 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 diluting the perovskite compound 1 with n-hexane to 200 ppm (μg / g), the peak wavelength of the emission spectrum measured by the quantum yield measuring device was 521 nm.

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

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

[Example 6]

After 10 mg of 3-[[2- (methacryloxy) ethyl] dimethylammonium] propionate was mixed in the dispersion liquid 1 containing the perovskite compound 1 and the solvent described in Example 1, the mixture was mixed. 30 mg of 2,2'-azobisisobutyronitrile. After substitution with nitrogen, the composition was polymerized while being stirred at 60 ° C. with a stirrer for 1 hour to obtain a composition. In the composition, the mass ratio is [perovskite compound 1] / [3-[[2- (methacryloxy) ethyl] dimethylammonium] propionate] = 0.013.

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

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

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

[Example 7]

Except that 3-[[2- (methacryloxy) ethyl] dimethylammonium] propionate was set to 20 mg, and the mass ratio was set to [Perovskite Compound 1] / [3-[[2 Except for-(methacryloxy) ethyl] dimethylammonium] propionate] = 0.0065, a composition was obtained in the same manner as in Example 6 above.

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

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

As shown in FIG. 3, when the composition mixed dispersion liquid 2 of Example 7 was used, the emission peak wavelength of the perovskite compound 1 and the emission peak wavelength of the perovskite compound 2 maintained a peak of 531 nm and a peak of 617 nm, respectively.

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

[Example 8]

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

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

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

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

[Example 9]

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

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

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

As shown in FIG. 4, when the composition mixed dispersion liquid 2 of Example 9 was used, the emission peak wavelength of the perovskite compound 1 and the emission peak wavelength of the perovskite compound 2 maintained a peak of 522 nm and a peak of 636 nm, respectively.

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

[Example 10]

After 5 µL of methacrylic acid was mixed with the dispersion liquid 2 containing the perovskite compound 2 and the solvent described in Example 1, 30 mg of 2,2'-azobisisobutyronitrile was mixed. After substitution with nitrogen, the composition was polymerized while being stirred at 60 ° C. with a stirrer for 1 hour to obtain a composition. In the composition, the mass ratio is [perovskite compound 2] / [methacrylic acid] = 0.026.

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

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

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

[Example 11]

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

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

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

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

[Example 12]

A composition was obtained in the same manner as in Example 10 except that methacrylic acid was set to 30 μL and the mass ratio was set to [Perovskite Compound 2] / [methacrylic acid] = 0.043.

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

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

As shown in FIG. 4, when the composition mixed dispersion liquid 1 of Example 12 was used, the emission peak wavelength of the perovskite compound 2 and the emission peak wavelength of the perovskite compound 1 maintained a peak at 626 nm and a peak at 520 nm, respectively.

(Luminescence peak wavelength (nm) of perovskite compound 1 before mixing)-(Luminescence peak wavelength (nm) of perovskite compound 1 after mixing) The absolute value is 3 nm, and (Perovskite compound before mixing The emission peak wavelength (nm) of 2)-(the emission peak wavelength (nm) of the perovskite compound 2 after mixing) has an absolute value of 4 nm.

[Example 13]

After 10 µL of 4-vinylbenzylamine was mixed with the dispersion liquid 2 containing the perovskite compound 2 and the solvent described in Example 1, 30 mg of 2,2'-azobisisobutyronitrile was mixed. After substitution with nitrogen, the composition was polymerized while being stirred at 60 ° C. with a stirrer for 1 hour to obtain a composition. In the composition, the mass ratio is [perovskite compound 2] / [4-vinylbenzylamine] = 0.013.

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

Next, methacrylic resin (PMMA, manufactured by Sumitomo Chemical Co., Ltd., Sumipecs ‧ methacrylic resin, MH, molecular weight about 120,000, specific gravity 1.2g / mL) was mixed with toluene until the methacrylic resin became 16.5% by mass. Then, it heated at 60 degreeC for 3 hours, and obtained the solution of the dissolved polymer.

0.15 g of a composition containing the above-mentioned perovskite compound 1, a polymer of an addition polymerizable compound having an ionic group and a solvent, 0.15 g of a dispersion liquid 2 containing a perovskite compound 2 and a solvent, and After 0.913 g of the solution was mixed, the solvent was evaporated by natural drying to obtain a composition having a concentration of 2,000 ppm (μg / g) of each perovskite compound.

The obtained composition was cut into 1 cm × 1 cm × 100 μm, and then a light emission spectrum was measured with a quantum yield measuring device. The results are shown in FIG. 4.

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

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

[Example 14]

Polysilazane (Durazane 1500 Slow Cure, manufactured by Merck Advanced Technology Materials Co., Ltd.) was mixed in a dispersion liquid 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 mixing 30 µL of methacrylic acid, 30 mg of 2,2'-azobisisobutyronitrile was mixed. After substitution with nitrogen, the composition was polymerized while being stirred at 60 ° C. with a stirrer for 1 hour to obtain a composition. In the composition, the mass ratio is [perovskite compound 1] / [based acrylic acid] = 0.0043.

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

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

As shown in FIG. 5, when the composition mixed dispersion liquid 2 of Example 14 was used, the emission peak wavelength of the perovskite compound 1 and the emission peak wavelength of the perovskite compound 2 maintained a peak of 517 nm and a peak of 639 nm, respectively.

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

The average Fisher's diameter of the aggregates contained in the composition was 1 μm.

[Example 15]

Polysilazane (Durazane 1500 Slow Cure, manufactured by Merck Advanced Technology Materials Co., Ltd.) was mixed with a dispersion liquid 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 mixing 20 µL of 4-vinylbenzylamine, 30 mg of 2,2'-azobisisobutyronitrile was mixed. After substitution with nitrogen, the composition was polymerized while being stirred at 60 ° C for 1 hour with a stirrer to obtain a composition. In the composition, the mass ratio is [perovskite compound 1] / [4-vinylbenzylamine] = 0.0067.

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

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

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

[Example 16]

Polysilazane (Durazane 1500 Slow Cure, manufactured by Merck Advanced Technology Materials Co., Ltd.) was mixed in a dispersion liquid 1 containing the perovskite compound 1 and the solvent described in Example 1. In the dispersion, the molar ratio was Si / Pb = 22.8. After mixing 5 µL of methacrylic acid, 30 mg of 2,2'-azobisisobutyronitrile was mixed. After substitution with nitrogen, the composition was polymerized while stirring at 60 ° C. with a stirrer for 1 hour to obtain a composition. In the composition, the mass ratio is [perovskite compound 1] / [methacrylic acid] = 0.026.

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

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

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

[Example 17]

Polysilazane (Durazane 1500 Slow Cure, manufactured by Merck Advanced Technology Materials Co., Ltd.) was mixed into a 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 mixing 10 µL of methacrylic acid, 30 mg of 2,2'-azobisisobutyronitrile was mixed. After substitution with nitrogen, the composition was polymerized while stirring at 60 ° C. with a stirrer for 1 hour to obtain a composition. In the composition, the mass ratio is [perovskite compound 2] / [methacrylic acid] = 0.013.

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

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

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

[Example 18]

Polysilazane (Durazane 1500 Slow Cure, manufactured by Merck Advanced Technology Materials Co., Ltd.) 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 mixing 30 µL of methacrylic acid, 30 mg of 2,2'-azobisisobutyronitrile was mixed. After substitution with nitrogen, the composition was polymerized while stirring at 60 ° C. with a stirrer for 1 hour to obtain a composition. In the composition, the mass ratio is [perovskite compound 2] / [methacrylic acid] = 0.0043.

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

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

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

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

The average Fisher's diameter of the aggregates contained in the composition was 0.3 μm.

[Comparative Example 1]

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

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

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

[Comparative Example 2]

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

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

0.1 mL of the above composition was mixed with 0.1 mL of a dispersion liquid 2 containing a perovskite compound 2 and a solvent in 0.8 mL of n-hexane. The mixed light emission spectrum was measured with a quantum yield measuring device. The results are shown in FIG. 6.

As shown in FIG. 6, in Comparative Example 2, a new emission peak wavelength of 571 nm is emitted, which is different from the emission peak wavelength of the perovskite compound 1 and the emission peak wavelength of the perovskite compound 2.

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

[Comparative Example 3]

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

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

0.1 mL of the above-mentioned composition was mixed with 0.1 mL of a dispersion liquid 2 containing a perovskite compound 2 and a solvent in 0.8 mL of n-hexane. The luminescence spectrum after mixing was measured with a quantum yield measurement device. The results are shown in FIG. 6.

As shown in Fig. 6, in Comparative Example 3, a new emission peak wavelength of 545 nm is emitted, which is different from the emission peak wavelength of the perovskite compound 1 and the emission peak wavelength of the perovskite compound 2.

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

The following Table 1 shows the composition of the compositions of Examples 1 to 18 and Comparative Examples 1 to 3, and the results of the evaluations 1 and 2 of the emission peaks when the two types of perovskite compounds were mixed. In Table 1, "(1) component / (2) component [mass ratio]" means the mass of the perovskite compound ((1) component) contained in the composition divided by the addition polymerizability with an ionic group The mass ratio of the mass of the compound or its polymer (component (2)).

From the above results, the composition in which the two kinds of perovskite compounds of Examples 1 to 18 of the present invention are mixed can maintain the inherent luminescence of each perovskite compound even if the kinds of perovskite compounds having different emission wavelengths are mixed wavelength. In contrast, in Comparative Examples 1 to 3, the emission peaks of new wavelengths are emitted, which are different from the intrinsic emission wavelength of each perovskite compound.

[Reference Example 1]

The composition described in Examples 1 to 18 was removed from the solvent as necessary, sealed in a glass tube or the like, and then placed between a blue light-emitting diode as a light source and a light guide plate. Backlight that converts blue light from a blue light-emitting diode into green or red light.

[Reference Example 2]

The composition described in Examples 1 to 18 was thinned after removing the solvent as necessary to obtain a resin composition. The sealed film was sandwiched between two barrier films and placed on the light guide plate. A backlight is produced by converting the blue light emitted from the blue light emitting diode placed on the side (side) of the light guide plate through the light guide plate to the green light or red light.

[Reference Example 3]

After the composition described in Examples 1 to 18 is removed as necessary, the composition can be placed near the light-emitting portion of the blue light-emitting diode to produce blue light or green light. The backlight.

[Reference Example 4]

The solvents described in Examples 1 to 18 are used to remove the solvent if necessary. After the resist is mixed, the solvent can be removed to obtain a wavelength conversion material. The obtained wavelength conversion material is arranged between a blue light emitting diode as a light source and a light guide plate or a rear stage of an OLED as a light source, and a backlight capable of converting blue light of the light source into green light or red light is manufactured.

[Reference Example 5]

The composition described in Examples 1 to 18 was mixed with conductive particles such as ZnS to form a film. One area layer was an n-type transport layer and the other area layer was a p-type transport layer to obtain an LED. When a current is passed, the holes of the p-type semiconductor and the electrons of the n-type semiconductor can cancel the charge in the perovskite compound on the joint surface and emit light.

[Reference Example 6]

A dense layer of titanium was laminated on the surface of a fluorine-doped tin oxide (FTO) substrate, a porous alumina layer was laminated thereon, and the composition described in Examples 1 to 18 was laminated thereon. After removing the solvent, It is laminated on top with 2,2'-7,7'-H- (N, N'-di-p-methoxyphenylamine) -9,9'-spirobifluorene (Spiro-OMeTAD) Layer, and a layer of silver (Ag) was stacked thereon to produce a solar cell.

[Reference Example 7]

After the composition described in Examples 1 to 18 is mixed with the resin, the resin composition containing the composition of the present invention can be obtained by removing the solvent and then forming the resin composition. Laser diode illumination that converts blue light emitted from a blue light-emitting diode onto the resin molded body into green light or red light and emits white light.

    [Possibility of industrial application]    

According to the present invention, a composition containing two kinds of perovskite compounds and showing two emission peaks can be provided. In addition, using the aforementioned composition, a film, a laminated structure, and a display can be provided.

Claims (16)

    A composition comprising a luminous composition containing the following (1) component and the following (2) component, wherein (1) component: a perovskite compound containing A, B, and X as constituent components, A type In the perovskite type crystal structure, the component located at each vertex of the hexahedron with B as the center is a monovalent cation; the X series represents the octahedron with B as the center in the perovskite crystal structure. The composition of each vertex is at least one anion selected from the group consisting of a halide ion and a thiocyanate ion; B is a perovskite-type crystal structure and is located in a hexahedron in which A is arranged at the vertex And the component in which X is arranged at the center of the octahedron at the vertex is a metal ion; (2) the component: an addition polymerizable compound having an ionic group or a polymer thereof.         The composition according to item 1 of the scope of patent application, wherein the component (2) is a radical polymerizable compound or an ion polymerizable compound, or a polymer thereof.         The composition according to item 1 of the scope of patent application, wherein the addition polymerizable compound having an ionic group is selected from acrylates and derivatives thereof having an ionic group, and methacrylic acid having an ionic group At least one of the group consisting of an ester and its derivative, and styrene and its derivative having an ionic group.         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, the component (1) and the component (2) ) The constituents are formed as aggregates.         The composition according to any one of claims 1 to 4 of the scope of patent application, further comprising at least one selected from the group consisting of the following (3) ingredients and the following (4) ingredients; (3) ingredients : Solvent (4) component: polymerizable compound or polymer thereof.         According to the composition described in any one of claims 1 to 4, the composition further contains the following (4 ') component, (1) component, (2) component, and (4) with respect to the total mass of the foregoing composition ') The total content of the components is 90% by mass or more. (4') Component: polymer.         The composition according to any one of claims 1 to 6 of the scope of patent application, further comprising the following component (5), which is selected from the group consisting of ammonia, amines and carboxylic acids, and salts or ions thereof. At least one type of group.         The composition according to any one of claims 1 to 7, further comprising the following component (6), which is selected from an organic compound having an amine group, an alkoxy group, and a silicon atom, and One or more compounds of the group consisting of silazane or a modified product thereof.         The composition according to item 8 of the scope of patent application, wherein the component (6) is polysilazane or a modified product thereof.         According to the composition described in any one of claims 1 to 9, the composition further includes the following component (1) -1, (1) -1 component: calcium having a different emission peak wavelength from the component (1) Titanium ore compound.         A film using the composition described in any one of claims 1 to 10 of the scope of patent application.         A laminated structure comprising the film described in claim 11 of the scope of patent application.         A light emitting device includes the laminated structure described in item 12 of the scope of patent application.         A display device includes the laminated structure described in item 12 of the scope of patent application.         A method for producing a composition, comprising the steps of dispersing the following (1) component in the following (3) component to obtain a dispersion liquid; mixing the obtained dispersion liquid with the following (2 ') component to obtain a mixed liquid A step of subjecting the obtained mixed solution to a polymerization treatment to obtain a mixed solution of a polymer containing an addition polymerizable compound having an ionic group, and a step of applying the addition polymerizable compound containing the obtained ionic group The step of mixing the polymer mixture with the following (4) components; (1) component: a perovskite compound with A, B, and X as constituent components, A is in a perovskite-type crystal structure and is located in The component of each vertex of a hexahedron with B as the center is a monovalent cation; the X series represents the component of each vertex of the octahedron with B as the center in the perovskite crystal structure, which is selected from halogenated At least one anion of a group consisting of a substance ion and a thiocyanate ion; B is a perovskite-type crystal structure and is located in a hexahedron with A at the vertex and an octahedron with X at the vertex The center component is a metal ion; (2 ') component: an ionic group Into the polymerizable compound; (3): a solvent; (4): a polymerizable compound or a polymer thereof.         According to the method for manufacturing a composition described in item 15 of the scope of patent application, the method further includes the step of mixing the following (1) -1 component in the mixed solution containing the aforementioned (4) component, and (1) -1 component: A perovskite compound having a wavelength different from the emission peak of the component (1).