JPWO2017221833A1 - Composition and compound - Google Patents

Abstract

In the present invention, the molar ratio [M / (M + B)] of A, B, X, and M as constituent components and the molar quantity of M divided by the total molar quantity of M and B is 0.7 or less And a composition containing a compound having a perovskite crystal structure. (A is a cesium ion, an organic ammonium ion, or an amidinium ion located at each vertex of a hexahedron centered on B in the perovskite crystal structure. B is a lead ion. M is a cesium ion. And at least one cation selected from the group consisting of cations of monovalent metal elements, and X represents a component located at each vertex of an octahedron centered on B in the perovskite crystal structure, Cl -, One or more anions selected from the group consisting of-, Br-, F-, I-and SCN-

Description

The present invention relates to compositions and compounds.
Priority is claimed on Japanese Patent Application No. 2016-126047, filed Jun. 24, 2016, the content of which is incorporated herein by reference.

  2. Description of the Related Art Organic-inorganic perovskite compounds that are organic cations, halide ions, and divalent metal ions are known. In recent years, there is a growing interest in the conductivity and light emission properties of compounds having a perovskite crystal structure having ions of a Group 14 element (Ge, Sn, and Pb) at metal ions.

  In particular, when the divalent metal ion is Pb (II), a strong light emission phenomenon at room temperature is observed in the range from the ultraviolet region to the red spectral region (Non-patent Document 1). In addition, it is also possible to adjust the emission wavelength depending on the type of halide ion (Non-patent Document 2).

M. Era, A. Shimizu and M. Nagano, Rep. Prog. Polym. Phys. Jpn. , 42, 473-474 (1999). L. Protesescu, S. Yakunin, M. I. Bodnarchuk, F. Krieg, R. Caputo, C. H. Hendon, R. X. Yang, A. Walsh, and M. V. Kovalenko, Nano Letter. 15, 3692-3696 (2015)

However, in order to industrially apply a compound having a perovskite crystal structure as described in the above-mentioned Non-Patent Document 1 or 2 as a light emitting material, further improvement of the light emission intensity or the quantum yield of the compound is required.
The present invention has been made in view of the above problems, and it is an object of the present invention to provide a compound having a perovskite crystal structure with high emission intensity, and a composition containing the compound with a high quantum yield.

  MEANS TO SOLVE THE PROBLEM In order to solve the said subject, the present inventors came to the following this invention, as a result of earnestly examining.

That is, the embodiment of the present invention includes the inventions of the following [1] to [11].
[1] Perovskite having A, B, X, and M as constituent components and having a molar ratio [M / (M + B)] of 0.7 or less of the molar quantity of M divided by the total molar quantity of M and B A composition comprising a compound having a crystalline structure of type. (A represents a component located at each vertex of a hexahedron centered at B, X represents a component located at each vertex of an octahedron centered at B, and A represents the perovskite crystal structure Cesium ion, organic ammonium ion, or amidinium ion, B is a lead ion, and M is a monovalent metal element other than cesium ion, which is located at each vertex of a hexahedron centered on B in And at least a part of M substitutes a part of B in the perovskite crystal structure, and X is in the perovskite crystal structure. Represents a component located at each vertex of the octahedron centered on B, and is at least one selected from the group consisting of chloride ion, bromide ion, fluoride ion, iodide ion and thiocyanate ion It is an anion.)
[2] The composition according to [1], wherein M is a cation of an alkali metal element.
[3] The composition according to [1] or [2], wherein M is a sodium ion or a lithium ion.
[4] The composition according to any one of [1] to [3], wherein A is an organic ammonium ion.
[5] The composition according to any one of [1] to [4], which contains a liquid as a medium in the composition.
[6] The composition according to any one of [1] to [4], which contains a resin as a medium in the composition.
[7] A perovskite having A, B, X, and M as constituent components, and the molar ratio of M divided by the total molar number of M and B (M) / (M + B) is 0.7 or less Compound having a crystalline structure
(A represents a component located at each vertex of a hexahedron centered at B, X represents a component located at each vertex of an octahedron centered at B, and A represents the perovskite crystal structure Cesium ion, organic ammonium ion, or amidinium ion, B is a lead ion, M is a sodium ion or lithium ion, and M is At least a part thereof substitutes a part of B in the perovskite type crystal structure, X represents a component located at each vertex of an octahedron centered on B in the perovskite type crystal structure, and is a chloride ion And at least one anion selected from the group consisting of bromide ion, fluoride ion, iodide ion and thiocyanate ion)
[8] A film comprising the composition according to [6] or the compound according to [7].
[9] A laminated structure having a layer containing the composition according to [6] or the compound according to [7].
[10] A light emitting device having the laminated structure according to [9] and a light source.
[11] A liquid crystal display comprising the light emitting device according to [10] and a liquid crystal panel.

  According to the present invention, it is possible to provide a composition in which a compound having a perovskite crystal structure with high luminous intensity and a compound having a perovskite crystal structure with a high quantum yield are dispersed in a medium.

It is sectional drawing which shows typically the structure of the laminated structure of this embodiment. It is sectional drawing which shows typically the structure of the liquid crystal display of this embodiment.

Hereinafter, the present invention will be described in detail by showing embodiments.
<Composition>
The present invention is a composition containing a compound having a perovskite crystal structure described later. The composition of the present invention is preferably a composition in which a compound having a perovskite crystal structure described later is dispersed in a medium.
The composition may have other components other than the above-described compound having a perovskite crystal structure. Other components include, for example, some impurities, and a compound having an amorphous structure containing A, B, X, and / or M as a component. As the impurities, for example, halides containing A, B and / or M, oxides and complex oxides of B and / or M, and other compounds containing A, B, X and / or M are mentioned. It can be mentioned.
As a composition in which a compound having a perovskite crystal structure is dispersed in a medium, a dispersion liquid composition in which a compound having a perovskite crystal structure described above is dispersed in a liquid, and a perovskite crystal structure described above The resin composition which the compound which it has is disperse | distributed in resin is mentioned.
Hereinafter, the compound having a perovskite crystal structure, the dispersion liquid composition, and the resin composition included in the composition according to the present invention will be described.

<Compound Having Perovskite Crystal Structure>
The compound having a perovskite crystal structure contained in the composition according to the present invention has A, B, X and M as constituents, and the molar quantity of M divided by the total molar quantity of M and B [M It is a compound which has a perovskite-type crystal structure whose value of / (M + B)] is 0.7 or less.
(A represents a component located at each vertex of a hexahedron centered at B, X represents a component located at each vertex of an octahedron centered at B, and A represents the perovskite crystal structure Cesium ion, organic ammonium ion, or amidinium ion, B is a lead ion, and M is a monovalent metal element other than cesium ion, which is located at each vertex of a hexahedron centered on B in And at least a portion of M substitutes a portion of B in the perovskite crystal structure.
X represents a component located at each vertex of the octahedron centered on B in the perovskite crystal structure, and is selected from the group consisting of chloride ion, bromide ion, fluoride ion, iodide ion and thiocyanate ion One or more anions. )

The compound having a perovskite crystal structure having A, B, X and M as a component is not particularly limited, and a compound having any one of a three-dimensional structure, a two-dimensional structure and a pseudo two-dimensional structure Good.
In the case of the three-dimensional structure, a perovskite-type crystal structure _is represented by _{AB (1-a) M a} X (3 + δ).
In the case of the two-dimensional structure, a perovskite-type crystal structure _is represented by _{A 2 B (1-a)} M a X (4 + δ).
a represents a molar ratio [M / (M + B)] obtained by dividing the molar quantity of M by the total molar quantity of M and B.
δ is a number that can be appropriately changed according to the charge balance of B and M, and is 0 or more and 0.7 or less. For example, when A is a monovalent cation, B is a divalent cation (Pb ion), M is a monovalent metal ion, and X is a monovalent anion, the compound is neutral (the charge is Δ can be selected to be 0).

Usually, the basic structure of the compound having a perovskite crystal structure is a three-dimensional structure or a two-dimensional structure.
For three-dimensional structure, the composition formula is expressed by A'B'X _'3. Here, A ′ represents an organic cation or an inorganic cation, B ′ represents a metal cation, and X ′ represents a halide ion or a thiocyanate ion.
In the case of a two-dimensional structure, the composition formula is represented by A ′ ₂ B′X ′ ₄ . Here, A ′, B ′ and X ′ represent the same meaning as described above.
For the three-dimensional structure, 'centered on the vertex X' B and has a three-dimensional network of corner-sharing octahedral represented by B'x _'6.
In the case of the above two-dimensional structure, an octahedron represented by B ′ X ′ ₆ having B ′ as a center and X ′ as an apex is two-dimensional by sharing X ′ of four apexes on the same plane. specific layer made of 'layers and a consisting of _6' continuous with BX that the forms stacked in an alternating manner.
B 'is a metal cation capable of octahedral coordination of X'.
A 'is located at each vertex of the hexahedron centered on B'.
In the present specification, the perovskite structure can be confirmed by an X-ray diffraction pattern.
In the case of a compound having a perovskite crystal structure of the three-dimensional structure, a peak derived from (hk1) = (001) or a position 2θ = 18 to 25 at a position of 2θ = 12 to 18 ° in an X-ray diffraction pattern. The peak derived from (hkl) = (100) is confirmed at the position of °. The peak derived from (hkl) = (001) is confirmed at the position of 2θ = 13-16 °, or the peak derived from (hkl) = (100) is confirmed at the position of 2θ = 20-23 ° Is more preferred.
In the case of a compound having a perovskite crystal structure of the two-dimensional structure, a peak derived from (hk1) = (002) is usually confirmed at a position of 2θ = 1 to 10 ° in the X-ray diffraction pattern, 2θ = 2 More preferably, a peak derived from (hkl) = (002) is identified at a position of -8 °.

  As a result of intensive investigations by the present inventors, in the compound having a perovskite crystal structure, the organic cation or the inorganic cation which is the component A 'is made a cesium ion, an organic ammonium ion or an amidinium ion (component A). A group consisting of a cation of a monovalent metal element, wherein the cation of the metal element which is the component is a lead ion (B component), and a plurality of the A component and / or the B component is other than a cesium ion. It has been found that emission intensity and quantum yield can be improved by substitution with one or more kinds of cations (M component) selected.

The compound of the present invention is preferably a compound having a perovskite crystal structure represented by the following general formula (1).
APb _(1−a) M _a X _{(3 + δ)} (0 <a ≦ 0.7, 0 ≦ δ ≦ 0.7) (1)
[In general formula (1), A is a cesium ion, an organic ammonium ion, or an amidinium ion, and M is a cation of at least one member selected from the group consisting of cations of monovalent metal elements excluding cesium ions. It is an ion. X is one or more anions selected from the group consisting of chloride ion, bromide ion, fluoride ion, iodide ion and thiocyanate ion. In the general formula (1), a is greater than 0 and 0.7 or less, and δ is 0 or more and 0.7 or less. ]

Generally, the basic structural form of perovskite is the ABX ₃ structure, which has a three-dimensional network of vertex-sharing BX ₆ octahedra. The B component in the ABX ₃ structure is a metal cation capable of taking octahedral coordination of the X anion. The A cation is located at each vertex of the hexahedron centered on the B atom, and is generally an organic cation or an inorganic cation. The X component of the ABX ₃ structure is usually a halide ion.

As a result of intensive studies by the present inventors, in the basic structure of the perovskite crystal structure represented by ABX ₃ above, the metal cation of the B component is lead, and a part of a plurality of lead ions in the three-dimensional network is It has been found that the emission intensity is improved by substituting the atom of
In the present invention, the compound having a perovskite crystal structure represented by the general formula (1) contains, as the A and B components, lead, M and X as main components. Here, M means an atom which substitutes a part of lead ion which is a metal cation. M substitutes the position at which the B component (lead ion) is present in the basic structure, or substitutes the position at which the A component is present, or exists in the lattice gap of the skeleton constituting the basic structure. May be However, it is preferable that at least a part of M substitute a part of B in the perovskite crystal structure.
Hereinafter, a compound having a perovskite-type crystal structure having A, B, X, and M as constituent components in the present invention will be described.

[A]
In the compound having a perovskite crystal structure, which is included in the composition according to the present invention, A is a cesium ion, an organic ammonium ion, or an amidinium ion.
In a compound having a perovskite crystal structure, when A is a cesium ion, an organic ammonium ion having 3 or less carbon atoms, or an amidinium ion having 3 or less carbon atoms, the perovskite crystal structure is generally _(1-a) has a three-dimensional structure represented by _Ma x ₃ ;

  Examples of the organic ammonium ion represented by A include organic ammonium ions represented by the following general formula (A1).

In general formula (A1), R ^{1 to} R ⁴ each independently represent a hydrogen atom, an alkyl group which may have an amino group as a substituent, or a cyclopropyl group which may have an amino group as a substituent Represents an alkyl group. However, all of R ^{1 to} R ⁴ will not be hydrogen atoms.

The alkyl group represented by R ^{1 to} R ⁴ may be linear or branched, and may have an amino group as a substituent.
The carbon atom number of the alkyl group represented by R ^{1 to} R ⁴ is usually 1 to 20, preferably 1 to 4, and more preferably 1 to 3.

The cycloalkyl group represented by R ^{1 to} R ⁴ may have an amino group as a substituent.
The carbon atom number of the cycloalkyl group represented by R ^{1 to} R ⁴ is usually 3 to 30, preferably 3 to 11, and more preferably 3 to 8.

The group represented by R ^{1 to} R ⁴ is preferably a hydrogen atom or an alkyl group.
By reducing the number of alkyl groups and cycloalkyl groups contained in the general formula (A1) and reducing the number of carbon atoms of the alkyl groups and cycloalkyl groups, a perovskite crystal structure of a three-dimensional structure with high emission intensity Can be obtained.
When the alkyl or cycloalkyl group has 4 or more carbon atoms, a compound having a two-dimensional and / or quasi two-dimensional (quasi-2D) perovskite crystal structure can be obtained in part or in whole. When two-dimensional perovskite-type crystal structures are stacked at infinity, they become equivalent to three-dimensional perovskite-type crystal structures (Reference: P. P. P. Boix et al., J. Phys. Chem. Lett. 2015, 6, 898-907 Such).
The total number of carbon atoms contained in the alkyl group represented by R ^{1 to} R ⁴ is preferably ^{1 to 4} , and the total number of carbon atoms contained in the cycloalkyl group represented by R ^{1 to} R ⁴ is It is preferable that it is 3-4. More preferably, R ¹ is an alkyl group having 1 to 3 carbon atoms, and R ^{2 to} R ⁴ are hydrogen atoms.

A is CH ₃ NH ₃ ⁺ (also referred to as methyl ammonium ion), C ₂ H ₅ NH ₃ ⁺ (also referred to as ethyl ammonium ion) or C ₃ H ₇ NH ₃ ⁺ (also referred to as propyl ammonium ion). Preferably, it is CH ₃ NH ₃ ⁺ or C ₂ H ₅ NH ₃ ⁺ , more preferably CH ₃ NH ₃ ⁺ .

As an amidinium ion represented by A, the amidinium ion represented by the following general formula (A2) is mentioned as an example, for example.
^{(R 5 R 6 N = CH} -NR 7 R 8) + ··· (A2)

In general formula (A2), R ^{5 to} R ⁸ each independently represent a hydrogen atom, an alkyl group which may have an amino group as a substituent, or a cyclo group which may have an amino group as a substituent Represents an alkyl group.

The alkyl group represented by R ^{5 to} R ⁸ may be linear or branched, and may have an amino group as a substituent.
The carbon atom number of the alkyl group represented by R ^{5 to} R ⁸ is usually 1 to 20, preferably 1 to 4, and more preferably 1 to 3.

The cycloalkyl group represented by R ^{5 to} R ⁸ may have an amino group as a substituent.
The carbon atom number of the cycloalkyl group represented by R ^{5 to} R ⁸ is usually 3 to 30, preferably 3 to 11, and more preferably 3 to 8.

The group represented by R ⁵ to R ^8, a hydrogen atom or an alkyl group.
By reducing the number of alkyl groups and cycloalkyl groups included in the general formula (A2) and reducing the number of carbon atoms of the alkyl groups and cycloalkyl groups, a perovskite crystal of a three-dimensional structure having high emission intensity Compounds having a structure can be obtained.
When the number of carbon atoms of the alkyl group or the cycloalkyl group is 4 or more, a compound having a two-dimensional and / or quasi two-dimensional (quasi-2D) perovskite crystal structure in part or in whole can be obtained. Further, the total number of carbon atoms contained in the alkyl group represented by R ^{5 to} R ⁸ is preferably 1 to 4, and the total of carbon atoms contained in the cycloalkyl group represented by R ^{5 to} R ⁸ The number is preferably 3 to 4. More preferably, R ⁵ is an alkyl group having 1 to 3 carbon atoms, and R ^{6 to} R ⁸ are hydrogen atoms.

[M]
M is at least one cation selected from the group consisting of cations of monovalent metal elements other than cesium ions.

  From the viewpoint of maintaining the crystal structure of the compound having a perovskite crystal structure and obtaining sufficient luminous intensity or quantum yield, M is preferably an alkali metal ion, and more preferably sodium ion or lithium ion. .

When M is a sodium ion or a lithium ion, the quantum yield of the composition in which the compound having the perovskite crystal structure is dispersed in the medium is improved. Furthermore, the light emission intensity of the compound having the perovskite crystal structure is also increased.
The compound having the perovskite crystal structure has a molar ratio of [M / (M + B)] where A, B, X and M are constituents and the molar quantity of M is divided by the total molar quantity of M and B. The compound which has a perovskite-type crystal structure which is 0.7 or less is mentioned.
In the above embodiment, A represents a component located at each vertex of a hexahedron centered at B, X represents a component located at each vertex of an octahedron centered at B, and A is the perovskite Cesium ion, organic ammonium ion, or amidinium ion located at each vertex of hexahedron centered on B in crystal structure of crystal form, B is lead ion, and M is sodium ion or lithium ion X represents a component located at each vertex of an octahedron centered on B in the perovskite crystal structure, and is a group consisting of chloride ion, bromide ion, fluoride ion, iodide ion and thiocyanate ion One or more anions selected.
Preferred embodiments and specific examples of the compound having a perovskite crystal structure are the preferred embodiments of a compound having a perovskite crystal structure contained in the composition according to the present invention except that M is a sodium ion or a lithium ion It is the same as the specific example.

[A]
a represents a molar ratio of the molar quantity of M divided by the total molar quantity of M and B [M / (B + M)].
From the viewpoint of maintaining the crystal structure of the compound having the perovskite crystal structure and obtaining a sufficient light emission intensity or quantum yield, a is greater than 0 and 0.7 or less. From the viewpoint of maintaining the crystal structure of the compound having the perovskite crystal structure and obtaining sufficient emission intensity or quantum yield, a is preferably 0.01 or more and 0.7 or less, and 0.02 or more, It is more preferably 5 or less, still more preferably 0.03 or more and 0.4 or less.
In another aspect of the present invention, a is preferably 0.08 or more and 0.2 or less.

[X]
X is one or more anions selected from the group consisting of chloride ion, bromide ion, fluoride ion, iodide ion and thiocyanate ion. Among these, chloride ion and bromide ion are preferably used.
When X contains a chloride ion or a bromide ion, the amount of the chloride ion or the bromide ion is preferably 10 to 100%, more preferably 30 to 100%, and more preferably 70 to 100 based on the total molar quantity of X. 100% is more preferable, and 80 to 100% or more is particularly preferable.
When X contains two or more types of halide ions, the content of chloride ions or bromide ions is preferably 10 mol% or more, more preferably 30 mol% or more, and 70 mol% with respect to the total molar number of X. The above is more preferable, and 80 mol% or more is particularly preferable.
Among them, X preferably contains a bromide ion. When X is two or more types of halide ions, the content ratio of the halide ions can be appropriately selected according to the emission wavelength.
In another aspect of the present invention, it is preferable that X contains chloride ion and bromide ion, and the content of chloride ion is 20 to 40 mol% and the content of bromide ion with respect to the total molar quantity of X. It is preferable that it is 50-80 mol%.
In still another aspect of the present invention, it is preferable that X contains a chloride ion and a bromide ion, and the molar ratio represented by [bromide ion / chloride ion] is 1.5 to 2.0. preferable.

Contained in the composition according to the present invention, a compound having a perovskite crystal _{structure, AB (1-a) M} a X (3 + δ) represented by a compound having a perovskite crystal structure having a three-dimensional structure As specific examples of 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 <y <3), CH ₃ NH ₃ Pb _(1-a) Li _a Br _{(3 + δ-y)} Cl _y ( 0 <a ≦ 0.7, 0 ≦ δ <0.7, 0 <y <3), (H ₂ N = CH—NH ₂ ) Pb _(1-a) Na _a Br _{(3 + δ)} (0 <a ≦ 0.7, −0.7 ≦ δ <0.7, (H ₂ N = CH—NH ₂ ) Pb _(1-a) Li _a Br _{(3 + δ)} (0 <a ≦ 0.7, −0. 7 ≦ δ <0.7, (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 ( _{-A) Na a Br (3 +} δ-y)
Cl _y (0 <a ≦ 0.7, −0.7 ≦ δ <0, 0 <y <3) and the like are mentioned as preferable. However, the above (3 + δ-y) is always 0 or more.

Contained in the composition according to the present invention, a compound having a perovskite crystal structure, represented by _{A 2 B (1-a)} M a X (4 + δ), perovskite type 2-dimensional structure of the crystal structure As a specific example of the compound which it has, (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Li _a Br _{(4 + δ)} (0 <a ≦ 0.7, −0.7 ≦ δ <0.7), (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Na _a Br _{(4 + δ)} (0 <a ≦ 0.7, −0.7 ≦ δ <0.7), (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Rb _a Br _{(4 + δ)} (0 <a ≦ 0.7, −0.7 ≦ δ <0.7), (C ₇ H ₁₅ NH ₃ ) ₂ Pb _{(1- a)} Na _{a Br (4 + δ) (} 0 <a ≦ 0.7, -0.7 ≦ δ <0.7), (C 7 H 15 NH 3) 2 Pb (1-a) Li a Br (4 + δ (0 <a ≦ 0.7, -0.7 ≦ δ <0.7), (C 7 H 15 NH 3) 2 Pb (1-a) Rb a Br (4 + δ) (0 <a ≦ 0.7 , −0.7 ≦ δ <0.7, (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 <0.7, 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 <0.7, 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 <0.7, 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 <0.7,0 < 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 <0.7,0 <y <4), (C 4 H 9 NH 3) 2 _{pb (1-a) Rb a} Br (4 + δ-y) Cl y be mentioned as (0 <a ≦ 0.7, -0.7 ≦ δ <0.7,0 <y <4) and the like are preferable. However, the above (4 + δ−y) is always 0 or more.

«Emission spectrum»
The compound having a perovskite crystal structure is a light emitter emitting fluorescence in the visible light wavelength region, and when X is a bromide ion, it is usually 480 nm or more, preferably 500 nm or more, more preferably 520 nm or more, and usually 700 nm or less Preferably, they emit fluorescence having a peak in the wavelength range of 600 nm or less, more preferably 580 nm or less.
The above upper limit value and lower limit value can be arbitrarily combined.
As another aspect of the present invention, when X in the compound having a perovskite crystal structure is a bromide ion, the peak of emitted fluorescence is usually 480 to 700 nm, preferably 500 to 600 nm, and 520 to 580 nm It is more preferable that
When X is an iodide ion, fluorescence having a peak in a wavelength range of usually 520 nm or more, preferably 530 nm or more, more preferably 540 nm or more, and usually 800 nm or less, preferably 750 nm or less, more preferably 730 nm or less Emit
The above upper limit value and lower limit value can be arbitrarily combined.
As another aspect of the present invention, when X in the compound having a perovskite crystal structure is an iodide ion, the peak of emitted fluorescence is usually 520 to 800 nm, preferably 530 to 750 nm, and 540 to 500 nm. More preferably, it is 730 nm.
When X is a chloride ion, fluorescence having a peak in a wavelength range of usually 300 nm or more, preferably 310 nm or more, more preferably 330 nm or more, and usually 600 nm or less, preferably 580 nm or less, more preferably 550 nm or less Emit
The above upper limit value and lower limit value can be arbitrarily combined.
In another aspect of the present invention, when X in the compound having a perovskite crystal structure is a chloride ion, the peak of emitted fluorescence is usually 300 to 600 nm, preferably 310 to 580 nm, and 330 to 580 nm. More preferably, it is 550 nm.

The maximum emission intensity of the compound having the perovskite crystal structure of the present invention is determined from the maximum intensity in the visible light wavelength range measured using a fluorometer and the transmittance of excitation light measured using an ultraviolet-visible absorptiometer. be able to.
As a fluorometer, for example, a fluorescence spectrophotometer RF-1500 (manufactured by Shimadzu Corporation) or a spectrofluorimeter FT-6500 (manufactured by JASCO Corporation) can be used. As an ultraviolet visible light absorptiometer, the ultraviolet visible light absorptiometer V-670 (made by JASCO Corporation) made from JASCO Corporation can be used, for example.
In the present invention, the maximum emission intensity of the compound can be a value corrected according to the following formula (S). In the following formula (S), Pmax is the maximum intensity in the visible light wavelength range, and Ep indicates the transmittance (%) of the excitation light.
Pmax / (100−Ep) × 100 (S)
One aspect of the present invention is a compound of the present invention containing bromide ion as the X component, wherein the maximum emission intensity near a wavelength of 530 nm is 10 or more.
The maximum emission intensity around the wavelength of 530 nm can be obtained by the following formula (S) -1.
[Maximum emission intensity around wavelength 530 nm / (100-transmittance of wavelength 430 nm)] × 100 (S) -1
In Formula (S) -1, the maximum intensity around the wavelength of 530 nm means the emission intensity of the peak with the highest intensity confirmed between the wavelengths of 520 to 540 nm.
The maximum emission intensity near the wavelength of 530 nm is preferably 10 to 70, and more preferably 15 to 60.
Another aspect of the present invention is a compound of the present invention containing a bromide ion and a chloride ion as the X component, wherein the maximum emission intensity near a wavelength of 500 nm is 40 or more.
The maximum emission intensity in the vicinity of the wavelength of 500 nm can be obtained by the following formula (S) -2.
[Maximum emission intensity around wavelength 500 nm / (100-transmittance of wavelength 430 nm)] × 100 (S) -2
In Formula (S) -2, the maximum intensity in the vicinity of a wavelength of 500 nm means the emission intensity of the highest intensity peak confirmed between the wavelengths of 490 and 510 nm.
The maximum emission intensity near the wavelength of 500 nm is preferably 40 to 100, and more preferably 60 to 80.
Yet another aspect of the present invention is a compound of the present invention containing bromide ion and iodide ion as the X component, wherein the maximum emission intensity near a wavelength of 540 nm is 10 or more.
The maximum emission intensity around the 540 nm can be obtained by the following formula (S) -3.
[Maximum emission intensity around wavelength 540 nm / (100-transmittance of wavelength 430 nm)] × 100 (S) -3
In Formula (S) -3, the maximum intensity in the vicinity of a wavelength of 500 nm means the emission intensity of the highest intensity peak confirmed between the wavelengths of 530 to 550 nm.
The maximum emission intensity near the wavelength of 540 nm is preferably 10 to 60, and more preferably 30 to 50.

  In the present invention, as described in << Method of calculating a >> in the present invention, the number of moles of M and B in the compound after synthesis is referred to as inductively coupled plasma mass spectrometer (hereinafter also referred to as ICP-MS) It can be a value calculated from the value measured by.

<< calculation method of a >>
The value of the molar ratio [M / (M + B)] of the molar quantity of M divided by the total molar quantity of M and B in the compound having the perovskite crystal structure is the compound having the perovskite crystal structure in the composition. The measurement can be performed after dissolution using a solvent such as nitric acid or N, N-dimethylformamide.
Specifically, the value of the molar ratio [M / (M + B)] is a value calculated according to the following formula (T). In the following formula (T), M mol represents the number of moles of M measured by ICP-MS, and Pb mol represents the number of moles of Pb measured by ICP-MS.
[M / (M + B)] = (Mmol) / (Mmol + Pbmol) (T)

In the present invention, it is preferable to set the value calculated by the << calculation method of a >> as “a” from the viewpoint that the substitution amount of M in the compound after synthesis can be calculated more accurately.
In addition, the value of a can be simply calculated from the value of the preparation ratio adjusted so that a in the compound of the present invention becomes a desired value when synthesizing the compound of the present invention.

<Dispersion composition>
The dispersion liquid composition according to the present invention is a composition in which the medium in the above-mentioned composition is a liquid, and the above-mentioned compound having a perovskite crystal structure is dispersed in the liquid. The quantum yield can be improved by using the above-described compound having the perovskite crystal structure as a dispersion liquid composition.
In the present specification, the term "liquid" refers to a substance that is in a liquid state at 1 atm and 25 ° C.

The dispersion composition may contain other components other than the compound having a perovskite crystal structure and the liquid described above. Examples of the component include impurities, a compound having an amorphous structure containing A, B, X, and / or M as a component, and a capping ligand.
As the impurities, for example, halides containing A, B and / or M, oxides and complex oxides of B and / or M, and other compounds containing A, B, X and / or M are mentioned. It can be mentioned. The other components are preferably 10% by mass or less based on the total mass of the dispersion composition.

The liquid (excluding resin) contained in the dispersion liquid composition is not particularly limited as long as it is a liquid that can disperse the above-described compound having a perovskite crystal structure.
It is preferable that the liquid (excluding the resin) contained in the dispersion liquid composition does not easily dissolve the above-described compound having a perovskite crystal structure.
Examples of the liquid (excluding resin) contained in the dispersion composition include methyl formate, ethyl formate, propyl formate, esters of pentyl formate, methyl acetate, ethyl acetate, pentyl acetate, etc .; -Ketones such as butyrolactone, N-methyl-2-pyrrolidone, acetone, dimethyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone and methylcyclohexanone; diethyl ether, methyl tert-butyl ether, diisopropyl ether, dimethoxymethane, dimethoxyethane, 1 , 4-dioxane, 1,3-dioxolane, 4-methyldioxolane, tetrahydrofuran, methyltetrahydrofuran, ethers such as anisole, phenetole; methanol, ethanol, 1-propane Panol, 2-propanol, 1-butanol, 2-butanol, tert-butanol, 1-pentanol, 2-methyl-2-butanol, methoxypropanol, diacetone alcohol, cyclohexanol, 2-fluoroethanol, 2,2,2, Alcohols such as 2-trifluoroethanol and 2,2,3,3-tetrafluoro-1-propanol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, triethylene glycol Glycol ethers such as dimethyl ether; organic solvents having an amide group such as N, N-dimethylformamide, acetamide, N, N-dimethylacetamide; acetonitrile; Organic solvents having a nitrile group such as ronitrile, propionitrile and methoxyacetonitrile; Organic solvents having a hydrocarbon group such as ethylene carbonate and propylene carbonate; Organic solvents having a halogenated hydrocarbon group such as methylene chloride, dichloromethane and chloroform Organic solvents having a hydrocarbon group such as n-pentane, cyclohexane, n-hexane, benzene, toluene, xylene and the like; dimethyl sulfoxide and the like.
Among them, esters of methyl formate, ethyl formate, propyl formate, pentyl formate, methyl acetate, ethyl acetate, pentyl acetate etc .; γ-butyrolactone, acetone, dimethyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methyl Ketones such as cyclohexanone; diethyl ether, methyl tert-butyl ether, diisopropyl ether, dimethoxymethane, dimethoxyethane, 1,4-dioxane, 1,3-dioxolane, 4-methyldioxolane, tetrahydrofuran, methyltetrahydrofuran, anisole, phenetole, etc. Organic solvents having a nitrile group such as ether, acetonitrile, isobutyronitrile, propionitrile, methoxyacetonitrile, etc .; Organic solvents having a carbonate group such as toluene carbonate and propylene carbonate; organic solvents having a halogenated hydrocarbon group such as methylene chloride, dichloromethane and chloroform; n-pentane, cyclohexane, n-hexane, benzene, toluene, xylene and the like An organic solvent having a hydrocarbon group is preferable because it is considered to be difficult to dissolve a compound having a perovskite crystal structure because of its low polarity, and an organic solvent having a halogenated hydrocarbon group such as methylene chloride, dichloromethane, chloroform and the like; Hydrocarbon-based organic solvents such as pentane, cyclohexane, n-hexane, benzene, toluene and xylene are more preferable.

  The dispersion composition according to the present invention may contain a capping ligand. The capping ligand is a compound which is adsorbed on the surface of the particle (compound having a perovskite crystal structure) and stably dispersed in the dispersion solvent, and as the capping ligand, for example, a general compound to be described later The ammonium salt represented by Formula (A3) and the compound which has a carboxy group represented by (A4) are mentioned. The dispersion composition according to the present invention may contain either one of the ammonium salt represented by the general formula (A3) and the compound having a carboxy group represented by the general formula (A4), both of them May be included.

  The dispersion composition may contain an ammonium salt represented by the general formula (A3).

In formula (A3), each of R ^{9 to} R ¹² independently may be a hydrogen atom, an alkyl group which may have an amino group as a substituent, or one amino group as a substituent It represents an unsaturated hydrocarbon group or a cycloalkyl group which may have an amino group as a substituent.

The alkyl group represented by R ^{9 to} R ¹² may be linear or branched, and may have an amino group as a substituent.
The carbon atom number of the alkyl group represented by R ^{9 to} R ¹² is usually 1 to 20, preferably 5 to 20, and more preferably 8 to 20.
The unsaturated hydrocarbon group represented by R ^{9 to} R ¹² may be linear or branched, and may have one amino group as a substituent. The carbon atom number of the unsaturated hydrocarbon group represented by R ^{9 to} R ¹² is usually 2 to 20, preferably 5 to 20, and more preferably 8 to 20.

The cycloalkyl group represented by R ^{9 to} R ¹² may have an amino group as a substituent.
The carbon atom number of the cycloalkyl group represented by R ^{9 to} R ¹² is usually 3 to 30, preferably 3 to 20, and more preferably 3 to 11.

R ^{9 to} R ¹² are preferably a hydrogen atom, an alkyl group or an unsaturated hydrocarbon group. As the unsaturated hydrocarbon group, an alkenyl group is preferable.

The ammonium salt represented by the general formula (A3) may be adsorbed on the surface of the compound having a perovskite crystal structure described above, or may be dispersed in a solvent. The counter anion of the ammonium salt, in particular limitation is not ^{Br -, Cl -, I -} , F - include a halide ion.
As the ammonium salt represented by the general formula (A3), a salt of n-octylamine and a salt of oleylamine are preferable.

The dispersion composition may contain a compound having a carboxy group represented by (A4).
R ¹³ -CO ₂ H (A4)

In general formula (A4), R ¹³ is an alkyl group which may have one carboxy group as a substituent, an unsaturated hydrocarbon group which may have one carboxy group as a substituent, or a substituent It represents a cycloalkyl group which may have one carboxy group as a group.

The alkyl group represented by R ¹³ may be linear or branched, and may have one carboxy group as a substituent. The carbon atom number of the alkyl group represented by R ¹³ is usually 1 to 20, preferably 5 to 20, and more preferably 8 to 20.
The unsaturated hydrocarbon group represented by R ¹³ may be linear or branched, and may have one carboxy group as a substituent. The carbon atom number of the unsaturated hydrocarbon group represented by R ¹³ is usually 2 to 20, preferably 5 to 20, and more preferably 8 to 20.

The cycloalkyl group represented by R ¹³ may have one carboxy group as a substituent.
The carbon atom number of the cycloalkyl group represented by R ¹³ is usually 3 to 30, preferably 3 to 20, and more preferably 3 to 11.

R ¹³ is preferably an alkyl group or an unsaturated hydrocarbon group. As the unsaturated hydrocarbon group, an alkenyl group is preferable.

The compound having a carboxy group represented by (A4) may be adsorbed on the surface of the above-mentioned compound having a perovskite crystal structure, or may be dispersed in a solvent.
The compound having a carboxy group represented by (A4) is preferably oleic acid.

The content of the compound having the above-mentioned perovskite crystal structure contained in the dispersion composition is not particularly limited, but it is difficult to aggregate the compound having the perovskite crystal structure, and the concentration quenching is prevented. From the viewpoint, the total content of the dispersion composition is preferably 50% by mass or less, more preferably 10% by mass or less, and 1% by mass from the viewpoint of obtaining a sufficient quantum yield. It is preferable to set it as ppm or more, and it is more preferable to set it as 10 mass ppm or more.
As another aspect of the present invention, the content of the compound having a perovskite crystal structure contained in the dispersion composition is 1 mass ppm or more and 50 mass% or less based on the total mass of the dispersion composition. It is preferable to set it as 10 mass ppm or more and 10 mass% or less.
In the present specification, the content of the compound having a perovskite crystal structure with respect to the total mass of the dispersion composition is, for example, ICP-MS, inductively coupled plasma emission spectrometry (hereinafter also referred to as ICP-AES). It can measure by analyzing the element which comprises the said perovskite-type crystal structure by an ion chromatograph etc. Moreover, a part of elements which comprise the said perovskite-type crystal structure are measured, and it calculates from molar ratio. It can also be measured by

The average particle diameter of the compound having the above-mentioned perovskite-type crystal structure dispersed in the dispersion composition is not particularly limited, but from the viewpoint of sufficiently maintaining the crystal structure, the average particle diameter is 1 nm The average particle diameter is preferably 10 μm or less from the viewpoint of making it difficult to precipitate a compound having a perovskite crystal structure, which is preferably 2 nm or more, more preferably 2 nm or more, and further preferably 3 nm or more The thickness is preferably 1 μm or less, and more preferably 500 nm or less.
As another aspect of the present invention, the average particle diameter of the compound having a perovskite crystal structure dispersed in the dispersion composition is preferably 1 nm to 10 μm, and more preferably 2 nm to 1 μm. And 3 nm to 500 nm are more preferable.
In the present specification, the average particle diameter of the compound having a perovskite crystal structure dispersed in the dispersion composition is, for example, a scanning electron microscope (hereinafter also referred to as SEM), a transmission electron microscope ( Hereinafter, it can also be measured by TEM. Specifically, the particle sizes of the 20 compounds having the perovskite crystal structure dispersed in the dispersion composition are observed by TEM or SEM, and the average value thereof is calculated. The average particle diameter can be determined.

The particle size distribution of the compound having the above-mentioned perovskite crystal structure contained in the dispersion composition is not particularly limited, but from the viewpoint of sufficiently maintaining the crystal structure, the median diameter D50 is 3 nm or more Is preferably 4 nm or more, more preferably 5 nm or more, and from the viewpoint of making it difficult to precipitate a compound having a perovskite crystal structure, it is preferably 5 μm or less, and 500 nm or less Is more preferably 100 nm or less.
In another aspect of the present invention, in the particle size distribution of the compound having a perovskite crystal structure contained in the dispersion composition, the median diameter D50 is preferably 3 nm to 5 μm, and more preferably 4 nm to 500 nm. Preferably, 5 nm to 100 nm is more preferable.
In the present specification, the particle size distribution of the compound having a perovskite crystal structure dispersed in the dispersion composition can be measured by, for example, TEM or SEM. Specifically, the particle sizes of the 20 compounds having the perovskite crystal structure dispersed in the dispersion liquid composition are observed by TEM or SEM, and the distribution of the particles of the median diameter D50 can be obtained.

«Calculation of a»
In the dispersion composition according to the present invention, the molar ratio [M / (M + B)] obtained by dividing the molar quantity of M described above by the total molar quantity of M and B is ICP-MS (ELAN DRC II, Perkin Elmer Product) to measure. The compound having a perovskite crystal structure in the dispersion composition can be measured after being dissolved using a solvent such as nitric acid or N, N-dimethylformamide. The specific calculation method is the same as the calculation method of the compound having a perovskite crystal structure described above.

«Measurement of quantum yield»
The quantum yield of the dispersion composition according to the present invention should be measured using an absolute PL quantum yield measurement apparatus (manufactured by Hamamatsu Photonics, trade name C9920-02, measurement conditions: excitation light 450 nm, room temperature, under the atmosphere) Can. The quantum yield of the dispersion composition is adjusted and measured so that the compound having the perovskite crystal structure has a concentration of 100 to 2000 ppm (μg / g) with respect to the total mass of the dispersion composition. Can.
One aspect of the present invention is a composition comprising a compound of the present invention containing an organic ammonium ion as component A, wherein the quantum yield measured by the above method is 80% or more.
The quantum yield is preferably 80 to 100%, and more preferably 85 to 100%.
Another aspect of the present invention is a composition comprising a compound of the present invention containing cesium ion as component A, wherein the quantum yield measured by the above method is 40% or more.
The quantum yield is preferably 40 to 100%, and more preferably 40 to 80%.

<Resin composition>
The resin composition according to the present invention is a composition in which the medium in the above-described composition is a resin, and the above-described compound having a perovskite crystal structure is dispersed in the resin. The quantum yield can be improved by using the above-described compound having a perovskite crystal structure as a resin composition.
In the present specification, "resin" means an organic polymer compound.
The resin composition may have other components other than the above-described compound having the perovskite crystal structure and the resin. The other components are the same as the other components which may be contained in the above-mentioned dispersion composition according to the present invention. The other components are preferably 10% by mass or less based on the total mass of the dispersion composition.
The form of the resin composition according to the present invention is not particularly limited, and can be appropriately determined according to the use. The resin composition in which the compound having the perovskite crystal structure is dispersed may be formed into a film, or may be formed into a plate.

In the resin composition according to the present invention, the resin in which the compound having the perovskite crystal structure is dispersed is not particularly limited. Those having low solubility in the compound are preferred.
Examples of the resin include polystyrene and methacrylic resin.

The amount of the compound having a perovskite crystal structure contained in the resin composition is not particularly limited, but from the viewpoint of making it difficult to aggregate the compound having a perovskite crystal structure and the viewpoint of preventing concentration quenching, The content is preferably 50% by mass or less, more preferably 10% by mass or less, based on the total mass of the resin composition, and from the viewpoint of obtaining a sufficient quantum yield, 1% by mass or more Preferably, 10 mass ppm or more is more preferable.
As another aspect of this invention, content of the compound which has the said perovskite type crystal structure contained in a resin composition shall be 1 mass ppm or more and 50 mass% or less with respect to the total mass of the said resin composition. It is preferable that it is 10 mass ppm or more and 10 mass% or less.
In the present specification, the content of the compound having a perovskite crystal structure relative to the total mass of the resin composition can be measured, for example, by ICP-MS.

  The average particle diameter of the compound having a perovskite crystal structure dispersed in the resin composition is not particularly limited, but the compound having a perovskite crystal structure dispersed in the above-mentioned dispersion liquid composition It is similar to the average particle size of

  The particle size distribution of the compound having a perovskite crystal structure contained in the resin composition is not particularly limited, but the particle size distribution of a compound having a perovskite crystal structure dispersed in the above-mentioned dispersion liquid composition Is the same as

«Calculation of a»
In the resin composition according to the present invention, the value of the molar ratio [M / (M + B)] obtained by dividing the molar quantity of M described above by the total molar quantity of M and B is the dispersion composition according to the present invention. Similarly, it can measure using ICP-MS (ELAN DRCII, Perkin-Elmer make).

«Measurement of quantum yield»
The quantum yield of the resin composition according to the present invention is the same as that of the dispersion liquid composition according to the present invention described above, in an absolute PL quantum yield measuring apparatus (manufactured by Hamamatsu Photonics, trade name C9920-02, measurement conditions: excitation light At room temperature under the atmosphere).

<Production Method of Compound Having Perovskite Crystal Structure>
A compound having a perovskite crystal structure can be synthesized by a self-assembly reaction using a solution.
For example, a solution obtained by dissolving a compound containing Pb and the above X, a compound containing the above M and the above X, and a compound containing the above A and the above X in a solvent is applied to a substrate, and the solvent is By removing the compound, the compound having a perovskite crystal structure of the present invention can be synthesized.
As another method, a solution obtained by dissolving a compound containing Pb and the above-mentioned X and a compound containing the above-mentioned M and the above-mentioned X in a solvent is applied to a substrate, and the solvent is removed to form a coated film. And a solution of the compound containing A and X described above in a solvent is applied onto the coating film, and the solvent is removed to synthesize the compound having a perovskite crystal structure of the present invention. it can.
At the time of synthesis, the types and amounts of the compounds to be blended may be adjusted so that a and δ have desired values.

  As a coating method, a gravure coating method, a bar coating method, a printing method, a spray method, a spin coating method, a dip method, a die coating method, etc. may be mentioned.

  As a method for removing the solvent, one or more of vacuum, drying and blowing may be performed to evaporate the solvent. Drying may be performed at normal temperature or may be performed by heating. Although the temperature in the case of heating can be suitably determined in consideration of the time taken for drying and the heat resistance of the substrate, 50 to 200 ° C. is preferable, and 50 to 100 ° C. is more preferable.

The solvent used in the method for producing a compound is not particularly limited as long as it can dissolve the above-mentioned A, B, M, X, and other components, and, for example, it is contained in the above-mentioned dispersion liquid composition The same as the liquid (but excluding the resin).
Among them, N-methyl-2-pyrrolidone, N, N-dimethylformamide, acetamide, N, N-dimethylacetamide and the like from the viewpoint of easily securing the solubility of the above-mentioned A, B, M, X and other components. An organic solvent having an amido group of the following, and dimethyl sulfoxide are preferably used, and in particular, N, N-dimethylformamide is preferably used.
The organic solvent may have a branched structure or a cyclic structure, may have a plurality of functional groups such as -O-, -CO-, -COO-, -OH, etc., and the hydrogen atom is fluorine or the like It may be substituted by the halogen atom of

  The amount of the solvent in the solution used in the method for producing a compound having a perovskite crystal structure is preferably 50% by mass or more, and more preferably 90% by mass or more based on the total mass of the solution. .

<Method of Producing Dispersion Composition>
The dispersion composition according to the present invention can be manufactured by the method described below with reference to known documents (Nano Lett. 2015, 15, 3692-3696, ACSNano, 2015, 9, 453-4542 etc.).
For example, as a method for producing a dispersion composition according to the present invention, a compound containing B and X, a compound containing M and X, and a compound containing A or a compound containing A and X are dissolved in a solvent A manufacturing method (dispersion liquid composition) comprising a step of obtaining a solution, and a step of mixing the obtained solution with a solvent whose solubility in a compound having a perovskite crystal structure is lower than the solvent used in the step of obtaining the solution Of the first embodiment).
Further, a compound containing B and X, a compound containing M and X, and a compound containing A or a compound containing A and X are added to a high-temperature solvent and dissolved to obtain a solution; And a step of cooling the solution (the second embodiment of the dispersion composition).

First Embodiment of Dispersion Composition
Hereinafter, a compound containing B and X, a compound containing M and X, and a compound containing A or a compound containing A and X are dissolved in a solvent to obtain a solution, the obtained solution, and a perovskite And D. mixing with a solvent having a lower solubility than the solvent used in the step of obtaining the solution.
In addition, solubility means the solubility in the temperature which performs the process to mix.
The production method preferably includes the step of adding a capping ligand from the viewpoint of stably dispersing the compound having the perovskite crystal structure. The capping ligand is preferably added before the mixing step described above, and the capping ligand is added to the solution in which A, B, X and M are dissolved, and the solubility for the compound having the perovskite crystal structure is , A solution added to a solvent lower than the solvent used in the step of obtaining a solution, or a solution in which A, B, X and M are dissolved, and a compound having a perovskite crystal structure is used in the step of obtaining a solution It may be added to both lower solvents.
It is preferable that the manufacturing method includes a step of removing coarse particles by a method such as centrifugation or filtration after the above-mentioned mixing step. The size of the coarse particles to be removed by the removing step is preferably 10 μm or more, more preferably 1 μm or more, and still more preferably 500 nm or more.

In the step of mixing the solution described above with a solvent having a solubility in a compound having a perovskite crystal structure lower than that used in the step of obtaining the solution, (a) the solution is a compound having a perovskite crystal structure The solvent may be dropped into a solvent having a lower solubility than the solvent used in the step of obtaining a solution, and (b) the solvent used in the step of obtaining a solution with respect to the compound having a perovskite crystal structure. It may be a step of dropping a lower solvent than that, but from the viewpoint of enhancing the dispersibility, (a) is preferable.
Stirring at the time of dropping is preferable from the viewpoint of enhancing the dispersibility.
There is no particular limitation on the temperature in the step of mixing the solution and a solvent having a solubility in a compound having a perovskite crystal structure lower than the solvent used in the step of obtaining the solution, but the perovskite crystal structure is possessed. The range of 0 to 40 ° C. is preferable, and the range of 10 to 30 ° C. is more preferable, from the viewpoint of securing the ease of precipitation of the compound.

  At the time of production, the types and amounts of the compounds to be blended may be adjusted so that a and δ have desired values.

The two solvents having different solubilities in the compound having a perovskite crystal structure used in the above-mentioned production method are not particularly limited, and examples thereof include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, tert-butanol, 1-pentanol, 2-methyl-2-butanol, methoxypropanol, diacetone alcohol, cyclohexanol, 2-fluoroethanol, 2,2,2-trifluoroethanol, 2,2,2, Alcohols such as 3, 3-tetrafluoro-1-propanol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, triethylene glycol Glycol ethers such as cole dimethyl ether; organic solvents having an amide group such as N, N-dimethylformamide, acetamide, N, N-dimethylacetamide; dimethyl sulfoxide, methyl formate, ethyl formate, propyl formate, pentyl formate, Esters such as methyl acetate, ethyl acetate and pentyl acetate; γ-butyrolactone, N-methyl-2-pyrrolidone, acetone, dimethyl ketone, diisobutyl ketone, ketones such as cyclopentanone, cyclohexanone and methylcyclohexanone; diethyl ether, methyl-tert -Butyl ether, diisopropyl ether, dimethoxymethane, dimethoxyethane, 1,4-dioxane, 1,3-dioxolane, 4-methyldioxolane, tetrahydrofuran Ethers such as rofuran, methyltetrahydrofuran, anisole, phenetole and the like; acetonitrile, isobutyronitrile, propionitrile, organic solvents having a nitrile group such as methoxyacetonitrile, etc .; organic solvents having a carbonate group such as ethylene carbonate and propylene carbonate; methylene chloride An organic solvent having a halogenated hydrocarbon group such as dichloromethane or chloroform; and two organic solvents selected from the group consisting of an organic solvent having a hydrocarbon group such as n-pentane, cyclohexane, n-hexane, benzene, toluene, or xylene A solvent is mentioned.
The solvent used in the step of obtaining a solution, which is included in the production method, is preferably a solvent having a high solubility in a compound having a perovskite crystal structure, for example, methanol when performing the step at room temperature (10 ° C. to 30 ° C.) Ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, tert-butanol, 1-pentanol, 2-methyl-2-butanol, methoxypropanol, diacetone alcohol, cyclohexanol, 2-fluoroethanol Alcohols such as 2,2,2-trifluoroethanol and 2,2,3,3-tetrafluoro-1-propanol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol Over monoethyl ether acetate, glycol ethers such as triethylene glycol dimethyl ether; and dimethyl sulfoxide; N, N- dimethylformamide, acetamide, N, organic solvents having an amide group such as N- dimethylacetamide.
The solvent used in the mixing step, which is included in the production method, is preferably a solvent having a low solubility in a compound having a perovskite crystal structure, and, for example, methylphor when performing the step at room temperature (10 ° C. to 30 ° C.) Esters such as ethyl formate, propyl formate, pentyl formate, methyl acetate, ethyl acetate, pentyl acetate; γ-butyrolactone, N-methyl-2-pyrrolidone, acetone, dimethyl ketone, diisobutyl ketone, cyclopentanone, Ketones such as cyclohexanone and methyl cyclohexanone; diethyl ether, methyl tert-butyl ether, diisopropyl ether, dimethoxymethane, dimethoxyethane, 1,4-dioxane, 1,3-dioxolane, 4-methyldioxy An ether such as run, tetrahydrofuran, methyltetrahydrofuran, anisole, phenetole, etc .; an organic solvent having a nitrile group such as acetonitrile, isobutyronitrile, propionitrile, methoxyacetonitrile, etc .; an organic solvent having a carbonate group such as ethylene carbonate, propylene carbonate; Organic solvents having a halogenated hydrocarbon group such as methylene chloride, dichloromethane, chloroform and the like; and organic solvents having a hydrocarbon group such as n-pentane, cyclohexane, n-hexane, benzene, toluene, xylene and the like.

  In two types of solvents having different solubilities, the difference in solubility is preferably 100 μg / 100 g to 90 g / 100 g of solvent, and more preferably 1 mg / 100 g to 90 g / 100 g of solvent. For example, in the case of performing the mixing step at room temperature (10 ° C. to 30 ° C.) from the viewpoint of setting the difference in solubility to 100 μg / 100 g to 90 g of solvent / 100 g of solvent, the solvent used in the step of obtaining the solution is N, N- Organic solvents having an amide group such as dimethylacetamide and dimethyl sulfoxide, and the solvent used in the mixing step is an organic solvent having a halogenated hydrocarbon group such as methylene chloride, dichloromethane and chloroform; n-pentane, cyclohexane, n- It is preferable that it is an organic solvent which has hydrocarbon groups, such as hexane, benzene, toluene, and xylene.

Second Embodiment of Method of Producing Dispersion Composition
And a step of obtaining a solution by adding a compound containing B and X, a compound containing M and X, and a compound containing A or a compound containing A and X to a solution at high temperature to obtain a solution, and And a step of cooling the solution.
In the above production method, the perovskite compound according to the present invention can be precipitated according to the difference in solubility due to the difference in temperature to produce the perovskite compound according to the present invention.

The production method preferably includes the step of adding a capping ligand from the viewpoint of stably dispersing the perovskite compound.
It is preferable that the manufacturing method includes a step of removing coarse particles by a technique such as centrifugation or filtration after the step of cooling. The size of the coarse particles to be removed by the removal step is preferably 10 μm or more, more preferably 1 μm or more, and still more preferably 500 nm or more.

Here, the high-temperature solvent may be a solvent at a temperature at which the compound containing B and X and the compound containing A or the compound containing A and X dissolve, for example, a solvent at 60 to 600 ° C. Is preferable, and a solvent at 80 to 400 ° C. is more preferable.
The temperature for cooling is preferably -20 to 50 ° C, and more preferably -10 to 30 ° C.
The cooling rate is preferably 0.1 to 1500 ° C./min, and more preferably 10 to 150 ° C./min.

  The solvent used in the production method is particularly limited as long as it can dissolve the compound containing B and X, the compound containing M and X, and the compound containing A or the compound containing A and X. Although it is not a thing, the thing similar to the liquid (however, resin is remove | excluded) contained in said dispersion liquid composition is mentioned, for example.

As a method of taking out the perovskite compound from the dispersion liquid containing the perovskite compound, a method of recovering only the perovskite compound by performing solid-liquid separation may be mentioned.
Examples of the above-mentioned solid-liquid separation method include a method such as filtration and a method utilizing evaporation of a solvent.

<Method for Producing Resin Composition>
For example, as a method for producing a resin composition according to the present invention, a step of mixing the compound having the above-described perovskite crystal structure or the dispersion composition according to the present invention with a solution in which a resin is dissolved in a solvent. And a step of removing the solvent.
Moreover, the manufacturing method including the process of mixing the compound which has the above-mentioned perovskite type crystal structure, or the dispersion liquid composition which concerns on this invention, and a monomer, and polymerizing a monomer and obtaining a resin composition is mentioned. .

  A resin composition comprising the steps of: mixing the compound having the perovskite crystal structure described above or the dispersion composition according to the present invention with a solution in which a resin is dissolved in a solvent; and removing the solvent The method of manufacturing the object will be described.

In the step of mixing the compound having the perovskite crystal structure described above, or the dispersion composition according to the present invention, and the solution in which the solvent resin is dissolved (a) the compound having the perovskite crystal structure described above, or the present The dispersion liquid composition according to the invention may be dropped into a solution in which a resin is dissolved in a solvent, or (b) a solution in which a resin is dissolved in a solvent is a compound having a perovskite crystal structure described above, or the present invention It may be dropped to the dispersion composition according to the above, but from the viewpoint of enhancing the dispersibility, (a) is preferable.
Stirring is preferable from the viewpoint of enhancing the dispersibility when mixing.
In the step of mixing the above-mentioned perovskite compound or the dispersion composition according to the present invention and the resin dissolved in the solvent, the temperature is not particularly limited, but from the viewpoint of uniform mixing, 0 to 100 ° C. It is preferable that it is in the range of 10 to 80 ° C.

  As a method of removing the solvent, natural drying by standing at room temperature may be used, or drying under reduced pressure using a vacuum dryer or a method of evaporating the solvent by heating may be mentioned.

The solvent for dissolving the above-mentioned resin is not particularly limited as long as it is a solvent capable of dissolving the resin, but those which hardly dissolve the above-mentioned perovskite compound are preferable.
Examples of the solvent in which the above-mentioned resin is dissolved include the same ones as the liquid (excluding the resin) contained in the above-mentioned dispersion liquid composition.
Among them, esters such as methyl formate, ethyl formate, propyl formate, pentyl formate, methyl acetate, ethyl acetate, pentyl acetate; γ-butyrolactone, acetone, dimethyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methylcyclohexanone Ketones such as diethyl ether, methyl-tert-butyl ether, diisopropyl ether, dimethoxymethane, dimethoxyethane, 1,4-dioxane, 1,3-dioxolane, 4-methyldioxolane, ethers such as tetrahydrofuran, methyltetrahydrofuran, anisole, phenetole, etc. Organic solvents having a nitrile group such as acetonitrile, isobutyronitrile, propionitrile, methoxyacetonitrile, etc .; ethylene Carbonate organic solvents such as carbonate and propylene carbonate; organic solvents having a halogenated hydrocarbon group such as methylene chloride, dichloromethane and chloroform; hydrocarbon groups such as n-pentane, cyclohexane, n-hexane, benzene, toluene and xylene Organic solvents having a low polarity are considered to be difficult to dissolve the perovskite compound, and organic solvents having a halogenated hydrocarbon group such as methylene chloride, dichloromethane, chloroform and the like are preferable; n-pentane, cyclohexane, n-hexane, Organic solvents having a hydrocarbon group such as benzene, toluene, xylene and the like are more preferable.

  Hereinafter, a production method including a step of mixing a compound having a perovskite crystal structure or a dispersion composition according to the present invention and a monomer, and a step of polymerizing the monomer to obtain a resin composition will be described.

The step of mixing the compound having the perovskite crystal structure, or the dispersion composition according to the present invention, and the monomer comprises: (a) a compound having the above-mentioned perovskite crystal structure, or the dispersion composition according to the present invention The monomer may be added dropwise, or the monomer (b) may be added dropwise to the compound having the above-described perovskite crystal structure, or the dispersion composition according to the present invention, but from the viewpoint of enhancing the dispersibility, (a) Is preferred.
Stirring is preferable from the viewpoint of enhancing the dispersibility when mixing.
In the step of mixing the above-mentioned perovskite compound or the dispersion liquid composition according to the present invention and the monomer, the temperature is not particularly limited, but from the viewpoint of uniformly mixing, it is in the range of 0 to 100 ° C. Preferably, the temperature is in the range of 10 to 80 ° C.

  Styrene and methyl methacrylate are mentioned as a monomer used in the said manufacturing method.

In the above-mentioned production method, as a method of polymerizing the monomers, known polymerization reactions such as radical polymerization can be appropriately used. For example, in the case of radical polymerization, a radical polymerization initiator is added to a mixture of a compound having the above-mentioned perovskite crystal structure or the dispersion composition according to the present invention and a monomer to generate a radical, thereby generating a polymerization reaction. The polymerization reaction proceeds by generating radicals using
Although a radical polymerization initiator is not specifically limited, A radical photopolymerization initiator is mentioned.
Examples of the photoradical polymerization initiator include bis (2,4,6-trimethylbenzoyl) -phenylphosphinoxide and the like.

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

<Membrane>
The film according to the present invention is a film containing the resin composition according to the present invention described above, or a film containing a compound having a perovskite crystal structure according to the present invention described above.

The thickness of the film according to the present invention is usually 0.01 μm to 10 mm, preferably 0.1 μm to 1 mm, and more preferably 1 μm to 0.5 mm.
In the present specification, the thickness of the film can be obtained by measuring at arbitrary three points with a micrometer and calculating the average value thereof.

  The film according to the present invention may contain a single compound having a perovskite crystal structure or may contain two or more compounds.

<Method of producing membrane>
The membrane according to the present invention can be produced, for example, by a self-assembly reaction using a solution. Here, the self-assembly reaction using a solution is the same as the method for producing the compound according to the present invention described above.

As the other method of the manufacturing method of the film | membrane which concerns on this invention, the coating method which used the dispersion liquid composition for this invention is mentioned, for example.
Here, the dispersion composition containing the compound having a perovskite crystal structure according to the present invention is the same as the dispersion composition according to the present invention described above. The dispersion composition may be a composition containing the above-described resin composition according to the present invention.

As one form of the coating method using a dispersion liquid composition, the method of manufacturing the film | membrane which concerns on this invention by apply | coating a dispersion liquid composition to a board | substrate and removing a solvent is mentioned.
As another mode of the coating method using the dispersion composition, the dispersion composition further including a monomer is applied to a substrate, the solvent is removed, and the monomer is polymerized to produce the film according to the present invention. Methods are included.

<Laminated structure>
The laminate structure according to the present invention is a laminate structure having a layer containing the resin composition according to the present invention described above, or a laminate structure having a layer containing a compound having a perovskite crystal structure according to the present invention described above. It is.

The thickness of the layer containing the resin composition according to the present invention and the layer containing the compound having a perovskite crystal structure according to the present invention is usually 0.01 μm to 10 mm, and 0.1 μm to 1 mm. Preferably, it is 1 μm to 0.5 mm.
In the present specification, the thickness of the film can be obtained by measuring at arbitrary three points with a micrometer and calculating the average value thereof.

  The laminated structure according to the present invention may have only one layer or two or more layers containing the resin composition according to the present invention, and has a perovskite crystal structure according to the present invention The layer containing the compound may have only one layer or two or more layers.

  As layers other than the layer containing the resin composition according to the present invention, or the layer containing a compound having a perovskite crystal structure according to the present invention, which may be possessed by the laminated structure according to the present invention, a substrate, Barrier layers, light scattering layers and the like can be mentioned.

(substrate)
The substrate is not particularly limited, but a transparent substrate is preferable from the viewpoint of taking out emitted light. As a board | substrate, the flexible substrate comprised from a polyethylene terephthalate etc., a glass substrate is mentioned, for example.

(Barrier layer)
The barrier layer is a layer having a function of protecting a layer containing the resin composition according to the present invention or a layer containing a compound having a perovskite crystal structure according to the present invention from water vapor and the like in the air.
The barrier layer is not particularly limited, but a transparent layer is preferable from the viewpoint of extracting emitted light. As the barrier layer, for example, a known barrier layer such as a SiO ₂ film or an Al ₂ O ₃ film can be used.

(Light scattering layer)
The light scattering layer is a layer having a function of scattering emitted light.
The light scattering layer is not particularly limited, but a transparent layer is preferable from the viewpoint of taking out emitted light. As a light-scattering layer, the layer containing light-scattering particle | grains, such as a silica particle, an amplification diffusion film is mentioned, for example.

FIG. 1 is a cross-sectional view schematically showing the structure of the laminated structure of the present embodiment. In the first laminate structure 1a, the layer 10 containing the resin composition according to the present invention or the compound having the perovskite crystal structure according to the present invention is provided between the first substrate 20 and the second substrate 21. ing. The film 10 is sealed by the sealing layer 22.
One aspect of the present invention is a compound having a perovskite crystal structure according to the present invention, which is located between the first substrate 20, the second substrate 21, and the first substrate 20 and the second substrate 21. And a sealing layer, wherein the sealing layer is the first substrate 20 of the layer 10 containing the compound having the perovskite crystal structure, and the second substrate. The laminated structure 1 a is characterized in that it is disposed on a surface not in contact with the substrate 21.
Another aspect of the present invention is a laminated structure 1b in which a prism sheet 50, a light guide plate 60, and the first laminated structure 1a are laminated in this order.

<Method of Manufacturing Laminated Structure>
The method for producing the layer containing the resin composition according to the present invention and the layer containing the compound having a perovskite crystal structure according to the present invention is the same as the method for producing the film according to the present invention described above. Therefore, the laminated structure according to the present invention can be produced by combining the method for producing a film according to the present invention described above with a known method.

<Light-emitting device>
A light emitting device according to the present invention is a light emitting device having the laminated structure according to the present invention and a light source. When the laminated structure is irradiated with light emitted from a light source, it is absorbed by the layer containing the resin composition or the compound having the perovskite crystal structure, and the layer containing the resin composition or the compound having the perovskite crystal emits light It is an apparatus for extracting light emitted from a layer containing a resin composition or a compound having a perovskite crystal structure. In the light emitting device according to the present invention, a layer containing a resin composition or a compound having a perovskite crystal structure usually functions as a wavelength conversion light emitting layer.
One aspect of the present invention is a light emitting device 2 in which a prism sheet 50, a light guide plate 60, the first laminated structure 1a, and a light source 30 are laminated in this order.

  In the light emitting device according to the present invention, as the layer other than the above which the laminated structure according to the present invention may have, for example, a light reflecting member layer, a brightness enhancing layer, a prism sheet, a light guide plate, and a medium between elements A material layer is mentioned.

(light source)
The light source is not particularly limited, but a light source having a light emission wavelength of 600 nm or less is preferable from the viewpoint of emitting light from the layer containing the resin composition in the laminate structure or the compound having the perovskite crystal structure. Examples of light sources include light emitting diodes (LEDs) such as blue light emitting diodes, lasers, and EL.

  Specific examples of the light emitting device according to the present invention include an EL display and a liquid crystal display. In an EL display or liquid crystal display, a layer containing a resin composition or a compound having a perovskite crystal structure usually functions as a wavelength conversion light emitting layer.

  As another specific example of the light emitting device according to the present invention, illumination may be mentioned. White light emitting illumination can be realized by using a blue light emitting diode as a light source and causing a layer containing a resin composition or a compound having a perovskite crystal structure to function as a wavelength conversion light emitting layer.

<Liquid crystal display>
As shown in FIG. 2, the liquid crystal display 3 of the present embodiment includes a liquid crystal panel 40 and the light emitting device 2 of the present embodiment in this order from the viewing side. The light emitting device 2 includes the second stacked structure 1 b and the light source 30. The second stacked structure body 1 b further includes the prism sheet 50 and the light guide plate 60 in the first stacked structure body 1 a described above. The display may further comprise any suitable other member.
One aspect of the present invention is a liquid crystal display 3 in which a liquid crystal panel 40, a prism sheet 50, a light guide plate 60, the first laminated structure 1a, and a light source 30 are laminated in this order.

<Use>
Examples of applications of the compound having a perovskite crystal structure according to the present invention, and dispersion liquid compositions and resin compositions containing the same include, for example, wavelength conversion materials for EL displays and liquid crystal displays, and specifically, (1) The compound having the perovskite crystal structure of the present invention is placed in a glass tube or the like and sealed, and this is placed between the blue light emitting diode as a light source and the light guide plate along the end face (side face) of the light guide plate. Back light to convert blue light into green light and red light (backlight with on-edge method), and (2) a compound having a perovskite crystal structure according to the present invention is dispersed in a resin or the like to form a sheet A blue light emitting diode placed on the end surface (side surface) of the light guide plate by placing the sealed film sandwiched between two barrier films on the light guide plate Back light which converts blue light irradiated to the sheet through the light guide plate to green light or red light (back light of surface mounting method), (3) a compound having a perovskite crystal structure according to the present invention, resin Or the like, and disposed in the vicinity of the light emitting part of the blue light emitting diode, and a back light (on-chip type back light) for converting the irradiated blue light into green light and red light, and (4) The compound which has a perovskite type crystal structure is disperse | distributed in a resist, and it installs on a color filter, and the backlight which converts blue light irradiated from a light source into green light and red light is mentioned.

  Examples of applications of the composition containing the compound having a perovskite crystal structure according to the present invention include a wavelength conversion material for a laser diode, and specifically, the compound having a perovskite crystal structure of the present invention is included. The composition may be shaped and disposed at a stage subsequent to a blue light emitting diode as a light source to convert blue light into green light and red light to emit white light.

The compound having a perovskite crystal structure according to the present invention can be used, for example, as a material of a light emitting layer of an LED.
As an LED containing a compound having a perovskite crystal structure according to the present invention, for example, a compound having a perovskite crystal structure according to the present invention and a conductive particle such as ZnS are mixed and laminated in a film shape. Type transport layer is stacked, and the other side is stacked with a p-type transport layer, and by passing current, the holes of the p-type semiconductor and the electrons of the n-type semiconductor form the perovskite crystal structure of the junction surface. There is a method of emitting light by canceling the charge in the compound which it has.

Furthermore, the compound having a perovskite crystal structure according to the present invention can be used as an electron transporting material contained in the active layer of a solar cell.
The configuration of the solar cell is not particularly limited, and includes, for example, a fluorine-doped tin oxide (FTO) substrate, a titanium oxide dense layer, a porous aluminum oxide layer, and a compound having a perovskite crystal structure according to the present invention Active layer, hole transport layer such as 2,2 ′, 7,7′-tetrakis- (N, N′-di-p-methoxyphenylamine) -9,9′-spirobifluorene (Spiro-OMeTAD), and silver (Ag) A solar cell having electrodes in this order.
The titanium oxide dense layer has a function of electron transport, an effect of suppressing the roughness of FTO, and a function of suppressing reverse electron transfer.
The porous aluminum oxide layer has a function of improving the light absorption efficiency.
The compound having a perovskite crystal structure according to the present invention contained in the active layer plays a role of charge separation and electron transport.

  Hereinafter, the present invention will be more specifically described based on examples and comparative examples, but the present invention is not limited to the following examples.

(Synthesis of Dispersion Composition Containing Compound Having Perovskite Crystal Structure)
Example 1
Mix 0.32 mmol of methyl ammonium bromide (CH ₃ NH ₃ Br), 0.388 mmol of lead bromide (PbBr ₂ ), 0.012 mmol of sodium bromide (NaBr), 40 μL of n-octylamine, 1 mL of oleic acid and 10 mL of DMF The solution was made.
Then, 4 mL of the solution was added to the toluene while stirring 20 mL of the toluene with a magnetic stirrer. After stirring for 1 hour, the precipitate was separated by centrifugation at 10000 rpm for 10 minutes to obtain a dispersion liquid composition containing a supernatant compound having a perovskite crystal structure.

Example 2
A dispersion composition containing a compound having a perovskite crystal structure is obtained in the same manner as in Example 1 except that lead bromide (PbBr ₂ ) is 0.38 mmol and sodium bromide (NaBr) is 0.02 mmol. The

[Example 3]
A dispersion liquid composition containing a compound having a perovskite crystal structure is obtained in the same manner as in Example 1 except that lead bromide (PbBr ₂ ) is 0.36 mmol and sodium bromide (NaBr) is 0.04 mmol. The
When the X-ray diffraction pattern was measured by an X-ray diffraction measurement apparatus (XRD, Cu Kα ray, X'pert PRO MPD, manufactured by Spectris), a peak derived from (hk1) = (001) was obtained at a position of 2θ = 14 °. It was confirmed to have a three-dimensional perovskite-type crystal structure.

Example 4
Mix 0.32 mmol of methyl ammonium bromide (CH ₃ NH ₃ Br), 0.388 mmol of lead bromide (PbBr ₂ ), 0.012 mmol of lithium bromide (LiBr), 40 μL of n-octylamine, 1 mL of oleic acid, and 10 mL of DMF The solution was made.
Then, 4 mL of the solution was added to the toluene while stirring 20 mL of the toluene with a magnetic stirrer. After stirring for 1 hour, the precipitate was separated by centrifugation at 10000 rpm for 10 minutes to obtain a dispersion liquid composition containing a supernatant compound having a perovskite crystal structure.

[Example 5]
A dispersion liquid composition containing a compound having a perovskite crystal structure is obtained in the same manner as in Example 4 except that lead bromide (PbBr ₂ ) is changed to 0.38 mmol and lithium bromide (LiBr) 0.02 mmol. The

[Example 6]
A dispersion liquid composition containing a compound having a perovskite crystal structure is obtained in the same manner as in Example 4 except that lead bromide (PbBr ₂ ) is 0.36 mmol and lithium bromide (LiBr) is 0.04 mmol. The

Comparative Example 1
A solution was prepared by mixing 0.32 mmol of methyl ammonium bromide (CH ₃ NH ₃ Br), 0.4 mmol of lead bromide (PbBr ₂ ), 40 μL of n-octylamine, 1 mL of oleic acid and 10 mL of DMF.
Next, 4 mL of the solution was added to toluene while stirring 20 mL of toluene with a magnetic stirrer. After stirring for 1 hour, the precipitate was separated by centrifugation at 10000 rpm for 10 minutes to obtain a dispersion liquid composition containing a supernatant compound having a perovskite crystal structure.
When the X-ray diffraction pattern was measured by an X-ray diffraction measurement apparatus (XRD, Cu Kα ray, X'pert PRO MPD, manufactured by Spectris), a peak derived from (hk1) = (001) was obtained at a position of 2θ = 14 °. It was confirmed to have a three-dimensional perovskite-type crystal structure.

(Measurement of M substitution amount)
One mL of DMF was added to 10 mL of the dispersion composition containing the compound having the perovskite crystal structure obtained in Examples 1 to 6 and Comparative Example 1 to dissolve the compound having the perovskite crystal structure. The number of moles of M (Na or Li) and B (Pb) in the solution after dissolution is measured by ICP-MS (ELAN DRC II, manufactured by Perkin Elmer), and M (Na) contained in the compound having a perovskite crystal structure The amount of Li or Li was applied to the formula of [M / (M + Pb)] to evaluate.

(Quantum yield measurement)
The quantum yield of the dispersion liquid composition containing the compound having a perovskite crystal structure obtained in Examples 1 to 6 and Comparative Example 1 was measured using an absolute PL quantum yield measuring apparatus (manufactured by Hamamatsu Photonics, trade name C9920-02, Measurement conditions: Measurement was carried out using an excitation light of 450 nm, room temperature, under the atmosphere).
The quantum yield was measured with the concentration of the compound having a perovskite crystal structure relative to the total mass of the dispersion composition set to 1000 ppm (μg / g).
A method of measuring the concentration of a compound having a perovskite crystal structure will be described. One mL of DMF was added to 10 mL of the dispersion composition containing the compound having the perovskite crystal structure obtained in Examples 1 to 6 and Comparative Example 1 to dissolve the compound having the perovskite crystal structure. The molar quantity of M (Zn) and B (Pb) in the obtained solution was measured by ICP-MS (ELAN DRCII, manufactured by Perkin Elmer), and the molar ratio was CH ₃ NH ₃ Pb _(1-a) M _a X The concentration of the compound having a perovskite crystal structure was measured by applying it to the equation of _{(3 + δ)} (0 <a ≦ 0.7, 0 ≦ δ ≦ 0.7) or CH ₃ NH ₃ PbBr ₃ .

  Table 1 below shows the constitution of the dispersion composition containing the compound having a perovskite crystal structure of Examples 1 to 6 and Comparative Example 1 and the quantum yield. In Table 1, [M / (M + Pb)] represents the molar ratio of the molar quantity of M measured by ICP-MS divided by the total molar quantity of M and B (lead ion).

  From the above results, the dispersion compositions of Examples 1 to 6 to which the present invention is applied have an excellent quantum yield as compared with the dispersion composition of Comparative Example 1 to which the present invention is not applied. That was confirmed.

(Synthesis of a compound having a perovskite crystal structure)
[Example 7]
A 2.5 cm × 2.5 cm size glass substrate was prepared. The glass substrate was subjected to ozone UV treatment.
Lead bromide (PbBr ₂ ) was dissolved in a solvent of N, N-dimethylformamide (hereinafter referred to as “DMF”) at 70 ° C. to prepare a lead bromide solution having a concentration of 0.1M. Similarly, sodium bromide (NaBr) was dissolved in a solvent of DMF at 70 ° C. to make a sodium bromide solution at a concentration of 0.1M.
Next, methyl ammonium bromide (CH ₃ NH ₃ Br) was dissolved in a solvent of DMF at 70 ° C. to make a methyl ammonium bromide solution at a concentration of 0.1 M. A solution was prepared by mixing the above-mentioned lead bromide solution and sodium bromide solution in a molar ratio of [Na / (Na + Pb)] 0.03.
Then, the solution was further mixed so that the molar ratio was [methyl ammonium bromide / (Na + Pb)] = 1.
The solution was applied by spin coating to the above glass substrate at a rotational speed of 1000 rpm, and dried at 100 ° C. in the air for 10 minutes to obtain a coated film of the compound.
When the X-ray diffraction pattern of the compound of the coating film is measured with an X-ray diffraction measurement apparatus (XRD, Cu Kα ray, X'pert PRO MPD, manufactured by Spectris), it is found that (hkl) = (2) at a position of 2θ = 14 °. It confirmed that it had a peak derived from 001) and had a three-dimensional perovskite crystal structure.

[Example 8]
A coated film of the compound was obtained by the same method as in Example 7 except that the molar ratio [Na / (Na + Pb)] was set to 0.05.
When the X-ray diffraction pattern of the compound of the coating film is measured with an X-ray diffraction measurement apparatus (XRD, Cu Kα ray, X'pert PRO MPD, manufactured by Spectris), it is found that (hkl) = (2) at a position of 2θ = 14 °. It confirmed that it had a peak derived from 001) and had a three-dimensional perovskite crystal structure.

[Example 9]
A coated film of the compound was obtained in the same manner as in Example 7 except that the molar ratio [Na / (Na + Pb)] was changed to 0.20.

[Example 10]
A coated film of the compound was obtained by the same method as in Example 7 except that the molar ratio [Na / (Na + Pb)] was set to 0.30.

Comparative Example 2
A 2.5 cm × 2.5 cm size glass substrate was prepared. The glass substrate was subjected to ozone UV treatment.
Lead bromide (PbBr ₂ ) was dissolved in a solvent of DMF at 70 ° C. to make a lead bromide solution at a concentration of 0.1M. Methyl ammonium bromide (CH ₃ NH ₃ Br) was dissolved in a solvent of DMF at 70 ° C. to make a methyl ammonium bromide solution at a concentration of 0.1M.
Then, the solution was mixed so that the molar ratio was (methyl ammonium bromide) / Pb = 1.
The solution was applied by spin coating to the above glass substrate at a rotational speed of 1000 rpm, and dried at 100 ° C. for 10 minutes to obtain a coated film of the compound.
When the X-ray diffraction pattern of the compound of the coating film is measured with an X-ray diffraction measurement apparatus (XRD, Cu Kα ray, X'pert PRO MPD, manufactured by Spectris), it is found that (hkl) = (2) at a position of 2θ = 14 °. It confirmed that it had a peak derived from 001) and had a three-dimensional perovskite crystal structure.

(Emission spectrum measurement)
The emission spectrum of the coating film of the compound having a perovskite crystal structure obtained in Examples 7 to 10 and Comparative Example 2 was measured using a fluorometer (manufactured by Shimadzu Corp., trade name: RF-1500, measurement condition: excitation light 430 nm, sensitivity) It measured using LOW). Moreover, the transmittance | permeability (%) of wavelength 430nm of the said coating film was measured using the ultraviolet visible light absorptiometer (The JASCO Corporation make, brand name V-670).
The comparison of the light emission intensity between the coated films was performed by correcting the maximum light emission intensity near the wavelength of 530 nm with the following formula (S) -1.
[Maximum emission intensity around wavelength 530 nm / (100-transmittance of wavelength 430 nm)] × 100 (S) -1
In Formula (S) -1, the maximum intensity around the wavelength of 530 nm means the emission intensity of the peak with the highest intensity confirmed between the wavelengths of 520 to 540 nm.

  Table 2 below describes the configuration of the compounds having the perovskite crystal structure of Examples 7 to 10 and Comparative Example 2 and the maximum emission intensity. In Table 1, [M / (M + Pb)] represents a molar ratio of the molar quantity of M divided by the total molar quantity of M and B (lead ion).

  From the above results, the compounds having the perovskite crystal structure according to the present invention of Examples 7 to 10 to which the present invention is applied are compared with the compounds having the perovskite crystal structure of Comparative Example 2 to which the present invention is not applied. It has been confirmed that the light emission intensity is excellent.

«Measurement by ICP-MS»
To the compound having the perovskite crystal structure on the glass substrate obtained in Example 8 was added 1 mL of nitric acid to dissolve the compound having the perovskite crystal structure. The solution after dissolution is adjusted to 10 ml in total with ion-exchanged water, and the amounts of Pb and M (Na) are measured by ICP-MS (ELAN DRCII, manufactured by Perkin-Elmer), and M (M (included in compounds having a perovskite crystal structure) The amount of Na) was estimated by fitting to the equation of [M / (M + B)].
As a result of measurement by ICP-MS, the value of [Na / (Pb + Na)] of Example 8 was 0.050.

(Synthesis of a compound having a perovskite crystal structure)
[Example 11]
A 2.5 cm × 2.5 cm size glass substrate was prepared. The glass substrate was subjected to ozone UV treatment.
Lead bromide (PbBr ₂ ) was dissolved in a solvent of N, N-dimethylformamide (hereinafter referred to as “DMF”) at 70 ° C. to prepare a lead bromide solution having a concentration of 0.1M. Similarly, lithium bromide (LiBr) was dissolved in a solvent of DMF at 70 ° C. to make a lithium bromide solution at a concentration of 0.1M.
Next, methyl ammonium bromide (CH ₃ NH ₃ Br) was dissolved in a solvent of DMF at 70 ° C. to make a methyl ammonium bromide solution at a concentration of 0.1 M. A solution was prepared by mixing the above-mentioned lead bromide solution and lithium bromide solution in a molar ratio of [Li / (Li + Pb)] 0.03.
Then, the solution was further mixed so that the molar ratio was [methyl ammonium bromide / (Li + Pb)] = 1.
The solution was applied by spin coating to the above glass substrate at a rotational speed of 1000 rpm, and dried at 100 ° C. in the air for 10 minutes to obtain a coated film of the compound.

[Example 12]
A coated film of the compound was obtained by the same method as in Example 11 except that the molar ratio [Li / (Li + Pb)] was set to 0.05.

[Example 13]
A coated film of the compound was obtained in the same manner as in Example 11 except that the molar ratio [Li / (Li + Pb)] was changed to 0.10.

(Emission spectrum measurement)
The emission spectrum of the coating film of the compound having a perovskite crystal structure obtained in each of Examples 11 to 13 and Comparative Example 2 was measured using a fluorometer (manufactured by Shimadzu Corporation, trade name: RF-1500, measurement conditions: excitation light 430 nm, sensitivity) It measured using LOW). Moreover, the transmittance | permeability (%) of wavelength 430nm of the said coating film was measured using the ultraviolet visible light absorptiometer (The JASCO Corporation make, brand name V-670).
The comparison of the light emission intensity between the coating films was performed by correcting the maximum light emission intensity near the wavelength of 530 nm with the following formula (S) -1.
[Maximum emission intensity around wavelength 530 nm / (100-transmittance of wavelength 430 nm)] × 100 (S) -1

  Table 3 below describes the configuration of the compound having a perovskite crystal structure of Examples 11 to 13 and Comparative Example 2 and the maximum emission intensity. In Table 3, [M / (M + Pb)] represents the molar ratio of the molar quantity of M calculated from the preparation amount of the raw materials divided by the total molar quantity of M and B (lead ion).

  From the above results, the compounds having the perovskite-type crystal structure according to the present invention of Examples 11 to 13 to which the present invention is applied are compared with the compounds having the perovskite-type crystal structure of Comparative Example 2 to which the present invention is not applied. It has been confirmed that the light emission intensity is excellent.

(Synthesis of a compound having a perovskite crystal structure)
Example 14
A 2.5 cm × 2.5 cm size glass substrate was prepared. The glass substrate was subjected to ozone UV treatment.
Lead bromide (PbBr ₂ ) was dissolved in a solvent of N, N-dimethylformamide (hereinafter referred to as “DMF”) at 70 ° C. to prepare a lead bromide solution having a concentration of 0.1M. Similarly, sodium bromide (NaBr) was dissolved in a solvent of DMF at 70 ° C. to make a sodium bromide solution at a concentration of 0.1M.
Methyl ammonium chloride (CH ₃ NH ₃ Cl) was then dissolved in a solvent of DMF at 70 ° C. to make a methyl ammonium chloride solution at a concentration of 0.1M. A solution was prepared by mixing the above-mentioned lead bromide solution and sodium bromide solution in a molar ratio of [Na / (Na + Pb)] 0.1.
Then, the solution was further mixed so that the molar ratio was [methyl ammonium chloride / (Na + Pb)] = 1.
The solution was applied by spin coating to the above glass substrate at a rotational speed of 1000 rpm, and dried at 100 ° C. in the air for 10 minutes to obtain a coated film of the compound.

[Example 15]
A 2.5 cm × 2.5 cm size glass substrate was prepared. The glass substrate was subjected to ozone UV treatment.
Lead bromide (PbBr ₂ ) was dissolved in a solvent of N, N-dimethylformamide (hereinafter referred to as “DMF”) at 70 ° C. to prepare a lead bromide solution having a concentration of 0.1M. Similarly, sodium bromide (NaBr) was dissolved in a solvent of DMF at 70 ° C. to make a sodium bromide solution at a concentration of 0.1M. Next, methyl ammonium iodide (CH ₃ NH ₃ I) was dissolved in a solvent of DMF at 70 ° C. to make a methyl ammonium iodide solution at a concentration of 0.1 M. A solution was prepared by mixing the above-mentioned lead bromide solution and sodium bromide solution in a molar ratio of [Na / (Na + Pb)] 0.1. Then, the solution was further mixed so that the molar ratio was [methylammonium iodide / (Na + Pb)] = 1.
The solution was applied by spin coating to the above glass substrate at a rotational speed of 1000 rpm, and dried at 100 ° C. in the air for 10 minutes to obtain a coated film of the compound.

[Example 16]
A 2.5 cm × 2.5 cm size glass substrate was prepared. The glass substrate was subjected to ozone UV treatment.
Lead bromide (PbBr ₂ ) was dissolved in a solvent of N, N-dimethylformamide (hereinafter referred to as “DMF”) at 70 ° C. to prepare a lead bromide solution having a concentration of 0.1M. Similarly, lithium bromide (LiBr) was dissolved in a solvent of DMF at 70 ° C. to make a lithium bromide solution at a concentration of 0.1M. Methyl ammonium chloride (CH ₃ NH ₃ Cl) was then dissolved in a solvent of DMF at 70 ° C. to make a methyl ammonium chloride solution at a concentration of 0.1M. A solution was prepared by mixing the above-mentioned lead bromide solution and lithium bromide solution in a molar ratio of [Li / (Li + Pb)] of 0.1. Then, the solution was further mixed so that the molar ratio was [methyl ammonium chloride / (Li + Pb)] = 1.
The solution was applied by spin coating to the above glass substrate at a rotational speed of 1000 rpm, and dried at 100 ° C. in the air for 10 minutes to obtain a coated film of the compound.

[Example 17]
A 2.5 cm × 2.5 cm size glass substrate was prepared. The glass substrate was subjected to ozone UV treatment.
Lead bromide (PbBr ₂ ) was dissolved in a solvent of N, N-dimethylformamide (hereinafter referred to as “DMF”) at 70 ° C. to prepare a lead bromide solution having a concentration of 0.1M. Similarly, lithium bromide (LiBr) was dissolved in a solvent of DMF at 70 ° C. to make a lithium bromide solution at a concentration of 0.1M. Next, methyl ammonium iodide (CH ₃ NH ₃ I) was dissolved in a solvent of DMF at 70 ° C. to make a methyl ammonium iodide solution at a concentration of 0.1 M. A solution was prepared by mixing the above-mentioned lead bromide solution and lithium bromide solution in a molar ratio of [Li / (Li + Pb)] of 0.1. Then, the solution was further mixed so that the molar ratio was [methylammonium iodide / (Li + Pb)] = 1.
The solution was applied by spin coating to the above glass substrate at a rotational speed of 1000 rpm, and dried at 100 ° C. in the air for 10 minutes to obtain a coated film of the compound.

Comparative Example 3
A 2.5 cm × 2.5 cm size glass substrate was prepared. The glass substrate was subjected to ozone UV treatment.
Lead bromide (PbBr ₂ ) was dissolved in a solvent of N, N-dimethylformamide (hereinafter referred to as “DMF”) at 70 ° C. to prepare a lead bromide solution having a concentration of 0.1M. Methyl ammonium chloride (CH ₃ NH ₃ Cl) was then dissolved in a solvent of DMF at 70 ° C. to make a methyl ammonium chloride solution at a concentration of 0.1M.
Then, the solution was further mixed such that [methyl ammonium chloride / Pb] = 1 in molar ratio.
The solution was applied by spin coating to the above glass substrate at a rotational speed of 1000 rpm, and dried at 100 ° C. in the air for 10 minutes to obtain a coated film of the compound.

Comparative Example 4
A 2.5 cm × 2.5 cm size glass substrate was prepared. The glass substrate was subjected to ozone UV treatment.
Lead bromide (PbBr ₂ ) was dissolved in a solvent of N, N-dimethylformamide (hereinafter referred to as “DMF”) at 70 ° C. to prepare a lead bromide solution having a concentration of 0.1M. Next, methyl ammonium iodide (CH ₃ NH ₃ I) was dissolved in a solvent of DMF at 70 ° C. to make a methyl ammonium iodide solution at a concentration of 0.1 M.
Then, the solution was further mixed such that [methylammonium iodide / Pb] = 1 in molar ratio.
The solution was applied by spin coating to the above glass substrate at a rotational speed of 1000 rpm, and dried at 100 ° C. in the air for 10 minutes to obtain a coated film of the compound.

(Emission spectrum measurement)
The emission spectrum of the coating film of the compound having a perovskite crystal structure obtained in Examples 14 and 16 and Comparative Example 3 was measured using a fluorometer (trade name FT-6500 manufactured by JASCO, measurement conditions: excitation light 430 nm, sensitivity It measured using HIgh). Moreover, the transmittance | permeability (%) of said coating film wavelength 430nm was measured using the ultraviolet visible absorptiometer (The JASCO Corporation make, brand name V-670).
The comparison of the light emission intensity between the coating films was performed by correcting the maximum light emission intensity near the wavelength of 500 nm with the following formula (S) -2.
[Maximum emission intensity around wavelength 500 nm / (100-transmittance of wavelength 430 nm)] × 100 (S) -2
In Formula (S) -2, the maximum intensity in the vicinity of a wavelength of 500 nm means the emission intensity of the highest intensity peak confirmed between the wavelengths of 490 and 510 nm.

(Emission spectrum measurement)
The emission spectrum of the coating film of the compound having a perovskite crystal structure obtained in Examples 15 and 17 and Comparative Example 4 was measured using a fluorometer (trade name FT-6500, manufactured by JASCO, measurement conditions: excitation light 430 nm, It measured using sensitivity HIgh). Moreover, the transmittance | permeability (%) of wavelength 430nm of the said coating film was measured using the ultraviolet visible light absorptiometer (The JASCO Corporation make, brand name V-670).
The comparison of the light emission intensity between the coated films was performed by correcting the maximum light emission intensity near the wavelength of 540 nm with the following equation (S) -3.
[Maximum emission intensity around wavelength 540 nm / (100-transmittance of wavelength 430 nm)] × 100 (S) -3
In the formula (S) -3, the maximum intensity around the wavelength of 540 nm means the emission intensity of the highest intensity peak confirmed between the wavelengths of 530 to 550 nm.

  Table 4 below describes the configurations of the compounds having the perovskite-type crystal structure of Examples 14 to 17 and Comparative Examples 3 to 4 and the maximum emission intensity. In Table 4, [M / (M + Pb)] represents the molar ratio of the molar quantity of M calculated from the preparation amount of the raw material divided by the total molar quantity of M and B (lead ion).

  From the above results, the compounds having the perovskite-type crystal structure according to the present invention of Examples 14 to 17 to which the present invention is applied are compared with the compounds having the perovskite-type crystal structure of Comparative Examples 3 to 4 to which the present invention is not applied. Thus, it was confirmed that the light emission intensity was excellent.

[Example 18]
10 mL of DMF was added to and mixed with cesium bromide (CsBr) so that the concentration of cesium was 2700 ppm (μg / g). Lead bromide _(PbBr 2) 0.38mmol, was prepared sodium bromide (NaBr) 0.02mmol, n- octylamine 88 [mu] L, oleic acid 1 mL, and the solution was mixed with the above-mentioned cesium bromide solution.
Next, 4 mL of the above solution was added to the toluene while 20 mL of toluene was stirred with a magnetic stirrer. After stirring for 1 hour, the precipitate was separated by centrifugation at 10000 rpm for 10 minutes to obtain a dispersion liquid composition containing a supernatant compound having a perovskite crystal structure.

Comparative Example 5
10 mL of DMF was added to and mixed with cesium bromide (CsBr) so that the concentration of cesium was 2700 ppm (μg / g). A solution was prepared by mixing 0.4 mmol of lead bromide (PbBr ₂ ), 88 μL of n-octylamine, 1 mL of oleic acid and the above cesium bromide solution.
Next, 4 mL of the above solution was added to the toluene while 20 mL of toluene was stirred with a magnetic stirrer. After stirring for 1 hour, the precipitate was separated by centrifugation at 10000 rpm for 10 minutes to obtain a dispersion liquid composition containing a supernatant compound having a perovskite crystal structure.

(Measurement of M substitution amount)
One mL of DMF was added to 10 mL of the dispersion composition containing the compound having the perovskite crystal structure obtained in Example 18 to dissolve the compound having the perovskite crystal structure. The number of moles of M (Na) and B (Pb) in the solution after dissolution was measured by ICP-MS (ELAN DRC II, manufactured by Perkin Elmer), and the amount of M (Na) contained in the compound having a perovskite crystal structure Was evaluated by fitting to the equation of [M / (M + Pb)].

(Quantum yield measurement)
The quantum yield of the dispersion composition containing the compound having a perovskite crystal structure obtained in Example 18 and Comparative Example 5 was measured using an absolute PL quantum yield measuring apparatus (manufactured by Hamamatsu Photonics, trade name C9920-02, excitation light). It measured using 450 nm and measurement conditions: room temperature and under the atmosphere). The concentration of the compound having a perovskite crystal structure with respect to the total mass of the dispersion composition was adjusted to 900 ppm (μg / g) to measure the quantum yield.

(Measurement of Perovskite Compound)
The concentrations of the perovskite compounds in the compositions obtained in Example 18 and Comparative Example 5 are determined by adding N, N-dimethylformamide to the dispersion containing the perovskite compound and the solvent, respectively. , ICP-MS (ELAN DRCII, manufactured by Perkin Elmer), and ion chromatograph.

  Table 5 below describes the configuration of the compound having a perovskite crystal structure of Example 18 and Comparative Example 5 and the quantum yield. In Table 5, [M / (M + Pb)] represents a molar ratio of the molar quantity of M divided by the total molar quantity of M and B (lead ion).

  From the above results, the dispersion liquid composition containing the compound having a perovskite crystal structure according to the present invention of Example 18 to which the present invention is applied corresponds to the compound having a perovskite crystal structure of Comparative Example 5 to which the present invention is not applied. It has been confirmed that the composition has an excellent quantum yield as compared to the dispersion composition contained.

[Reference Example 1]
The resin composition according to the present invention can be obtained by removing the liquid after mixing the dispersion composition according to the present invention and the resin according to Examples 1 to 6, and the resin composition according to the present invention can be obtained. After sealing, the backlight is disposed between the blue light emitting diode as a light source and the light guide plate to manufacture a backlight capable of converting blue light of the blue light emitting diode into green light and red light.

[Reference Example 2]
The resin composition according to the present invention can be obtained by removing the liquid and mixing it into a sheet after mixing the dispersion composition described in Examples 1 to 6 and the resin, and using this as a barrier film of 2 sheets. By placing a sealed film on the light guide plate, the blue light emitted from the blue light emitting diode placed on the end face (side surface) of the light guide plate to the sheet through the light guide plate can be green light or red light Manufacture backlights that can be converted to

[Reference Example 3]
The resin composition according to the present invention can be obtained by removing the solvent after mixing the dispersion liquid composition according to the present invention described in Examples 1 to 6 with the resin, and the resin composition according to the present invention can be obtained. A backlight is manufactured which can convert blue light emitted to green light or red light by being installed.

[Reference Example 4]
After the dispersion liquid composition according to the present invention described in Examples 1 to 6 and the resist are mixed, the wavelength conversion material can be obtained by removing the solvent. By arranging the obtained wavelength conversion material between the blue light emitting diode as a light source and the light guide plate, or after the OLED as a light source, a backlight capable of converting blue light of the light source into green light or red light Manufacture.

[Reference Example 5]
The dispersion liquid composition described in Examples 1 to 6 and conductive particles such as ZnS are mixed to form a film, an n-type transport layer is laminated on one side, and the other side is laminated by a p-type transport layer. Get When a current flows, holes in the p-type semiconductor and electrons in the n-type semiconductor can be made to emit light by canceling charges in the compound having a perovskite crystal structure at the junction surface.

[Reference Example 6]
A titanium oxide dense layer is laminated on the surface of a fluorine-doped tin oxide (FTO) substrate, a porous aluminum oxide layer is laminated thereon, and the dispersion composition described in Examples 1 to 6 is thereon. The perovskite layer is stacked using A hole transport layer is laminated, and a silver (Ag) layer is laminated thereon to fabricate a solar cell.

[Reference Example 7]
After the dispersion liquid composition containing the compound having the perovskite crystal structure according to the present invention described in Examples 1 to 6 and the resin are mixed, the solvent is removed and the perovskite crystal structure according to the present invention is formed. The resin composition containing the compound which it has can be obtained, By installing this in the back | latter stage of a blue light emitting diode, the blue light irradiated to the said resin molding from a blue light emitting diode is converted into green light and red light Manufacture laser diode illumination that emits white light.

According to the present invention, it is possible to provide a compound having a perovskite crystal structure having high luminous intensity, and a composition in which a compound having a perovskite crystal structure having a high quantum yield is dispersed in a medium. It becomes possible.
Therefore, the composition and compound according to the present invention can be suitably used in the field of luminescence related materials.

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

Claims (11)

Perovskite crystal structure wherein A, B, X, and M are constituents and the molar ratio of molar quantity of M divided by total molar quantity of M and B [M / (M + B)] is 0.7 or less A composition comprising a compound having:
(A represents a component located at each vertex of a hexahedron centered at B, X represents a component located at each vertex of an octahedron centered at B,
A is a cesium ion, an organic ammonium ion or an amidinium ion, which is located at each vertex of a hexahedron centered on B in the perovskite crystal structure,
B is lead ion,
M is at least one cation selected from the group consisting of cations of monovalent metal elements other than cesium ions, and at least a portion of M is a portion of B in the perovskite crystal structure. Replace.
X represents a component located at each vertex of the octahedron centered on B in the perovskite crystal structure, and is selected from the group consisting of chloride ion, bromide ion, fluoride ion, iodide ion and thiocyanate ion One or more anions. )   The composition according to claim 1, wherein the M is a cation of an alkali metal element.   The composition according to claim 1, wherein the M is a sodium ion or a lithium ion.   The composition according to any one of claims 1 to 3, wherein said A is an organic ammonium ion.   The composition according to any one of claims 1 to 4, wherein the composition contains a liquid as a medium.   The composition according to any one of claims 1 to 4, wherein the composition contains a resin as a medium. Perovskite crystal structure wherein A, B, X, and M are constituents and the molar ratio of molar quantity of M divided by total molar quantity of M and B [M / (M + B)] is 0.7 or less A compound having
(A represents a component located at each vertex of a hexahedron centered at B, X represents a component located at each vertex of an octahedron centered at B,
A is a cesium ion, an organic ammonium ion or an amidinium ion, which is located at each vertex of a hexahedron centered on B in the perovskite crystal structure,
B is lead ion,
M is a sodium ion or a lithium ion, and at least a part of M substitutes a part of B in the perovskite crystal structure.
X represents a component located at each vertex of the octahedron centered on B in the perovskite crystal structure, and is selected from the group consisting of chloride ion, bromide ion, fluoride ion, iodide ion and thiocyanate ion One or more anions. )   A film comprising the composition of claim 6 or the compound of claim 7.   A laminated structure having a layer comprising the composition according to claim 6 or the compound according to claim 7.   A light emitting device comprising the laminated structure according to claim 9 and a light source.   A liquid crystal display comprising the light emitting device according to claim 10 and a liquid crystal panel.

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