TW201819301A - Composition and compound - Google Patents

Abstract

The present invention relates to a composition comprising a compound having a perovskite-type crystal structure, the compound comprising A ion, B ion, X ion and M ion, wherein the molar ratio [M/(M+B)], which is calculated by dividing the molar number of M ion with the total molar number of M ion and B ion, is 0.7 or less, and wherein A ion is a cesium ion, an organic ammonium ion or an amidinium ion locating at each vertex of a hexahedron with B ion in the center, in the perovskite-type crystal structure; B ion is a lead ion; M ion is a monovalent metal element cation with exclusion of cesium ion; X ion is Cl-, Br-, F-, I- or SCN- locating at each vertex of an octahedron with B ion in the center, in the perovskite-type crystal structure.

Description

 Compositions and compounds  

This invention relates to compositions and compounds.

The present application claims the priority of Japanese Patent Application No. 2016-126047, filed on June 24, 2016 in Japan, the content of which is incorporated herein.

Conventionally, an organic-inorganic perovskite compound composed of a cation of a organic substance, a halide ion, and a divalent metal ion has been known. In recent years, there has been an increasing interest in the conductivity and luminescent properties of a compound having a perovskite crystal structure having ions of a group 14 element (Ge, Sn, and Pb) at a position of a metal ion.

In particular, when the divalent metal ion is Pb (II), a phenomenon of strong light emission at room temperature is observed in the range from the ultraviolet region to the red spectral region (Non-Patent Document 1). Further, the emission wavelength can be adjusted depending on the type of the halide ion (Non-Patent Document 2).

 [Previous Technical Literature]    [Non-patent literature]  

[Non-Patent Document 1] M. Era, A. Shimizu and M. Nagano, Rep. Prog. Polym. Phys. Jpn., 42, 473-474 (1999)

[Non-Patent Document 2] L. Protesescu, S. Yakunin, MI Bodnarchuk, F. Krieg, R. Caputo, CH Hendon, RX Yang, A. Walsh, And MV Kovalenko, Nano Letter. 15, 3692-3696 (2015)

However, in order to industrially apply a compound having a perovskite crystal structure as described in Non-Patent Document 1 or Non-Patent Document 2, it is required to further improve the luminescence intensity or quantum yield of the compound.

The present invention has been made in view of the above problems, and an object thereof is to provide a compound having a perovskite crystal structure having high luminescence intensity and a composition containing the above compound having a high quantum yield.

In order to solve the above problems, the inventors of the present invention have intensively studied and achieved the following invention.

That is, the embodiment of the present invention includes the inventions of the following [1] to [11].

[1] A composition comprising a compound having a perovskite crystal structure, wherein the compound is composed of A, B, X and M, and the number of moles of M is divided by the total number of moles of M and B. The value of the molar ratio [M/(M+B)] is 0.7 or less; (A represents the composition of each vertex of the hexahedron centered on B, and X represents the octahedron located at the center of B; The composition of the apex, A is a cerium ion, an organic ammonium ion or an amidinium ion located at each vertex of the hexahedron centered on B in the perovskite crystal structure; B is a lead ion; One or more cations of the group consisting of cations of a monovalent metal element other than cerium ions, at least a part of M is substituted for a part of B in the perovskite crystal structure; and X is located in the above-described perovskite crystal The component of each apex of the octahedron centered on B in the structure is one or more anions selected from the group consisting of chloride ions, bromide ions, fluoride ions, iodide ions, and thiocyanate ions. ).

[2] The composition according to [1], wherein the M is a cation of an alkali metal element.

[3] The composition according to [1] or [2] wherein the aforementioned 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] wherein the composition contains a liquid as a medium.

[6] The composition according to any one of [1] to [4] wherein the composition contains a resin as a medium.

[7] A compound having a perovskite crystal structure, wherein A, B, X and M are constituent components, and the number of moles of M is divided by the total number of moles of M and B to obtain a molar ratio [ The value of M/(M+B)] is 0.7 or less; (A represents a component located at each vertex of a hexahedron centered at B, and X represents a component located at each vertex of an octahedron centered at B, A a cerium ion, an organic ammonium ion or a cerium ion located at each vertex of a hexahedron centered on B in the aforementioned perovskite crystal structure; B is a lead ion; M is a sodium ion or a lithium ion, and at least M a part of the above-mentioned perovskite crystal structure is substituted for a part of B; X represents a component located at each vertex of the octahedron centered on B in the perovskite crystal structure, and is selected from chloride ion and bromine. One or more anions of the group consisting of a compound ion, a fluoride ion, an iodide ion, and a thiocyanate ion).

[8] A film comprising the composition according to [6] or the compound according to [7].

[9] A laminated structure comprising the composition according to [6] or the compound of [7]

[10] A light-emitting device comprising 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, a compound having a perovskite crystal structure having a high luminescence intensity and a composition having a high quantum yield and having a perovskite crystal structure dispersed in a medium can be provided.

1a‧‧‧1st buildup structure

1b‧‧‧2nd laminated structure

2‧‧‧Lighting device

3‧‧‧LCD display

10 ‧ ‧ layer

20‧‧‧1st substrate

21‧‧‧2nd substrate

22‧‧‧ Sealing layer

30‧‧‧Light source

40‧‧‧LCD panel

50‧‧‧ Picture

60‧‧‧Light guide plate

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

Fig. 2 is a schematic cross-sectional view showing the configuration of a liquid crystal display device of the present embodiment.

Hereinafter, the present invention will be described in detail by showing an embodiment.

 <composition>  

The present invention is a composition comprising 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 above composition may have other components than the above-described compound having a perovskite crystal structure. The other component may, for example, be a plurality of impurities, and a compound having an amorphous structure containing A, B, X and/or M as a constituent component. Examples of the impurities include halides containing A, B, and/or M; oxides of B and/or M, composite oxides; and other compounds containing A, B, X, and/or M.

Examples of the composition in which a compound having a perovskite crystal structure is dispersed in a medium may be a dispersion liquid composition in which a compound having a perovskite crystal structure is dispersed in a liquid, and the above-described perovskite crystal. The structural composition is a resin composition dispersed in a resin.

Hereinafter, a compound having a perovskite crystal structure, a dispersion composition, and a resin composition contained in the composition of the present invention will be described.

 <Compound having a perovskite crystal structure>  

The compound having a perovskite crystal structure contained in the composition of the present invention has A, B, X and M as constituent components, and the number of moles of M divided by the total number of M and B is obtained. A compound having a perovskite crystal structure having an ear ratio of [M/(M+B)] of 0.7 or less.

(A denotes a component located at each vertex of a hexahedron centered at B, X denotes a component located at each vertex of an octahedron centered at B, and A denotes a B in the perovskite crystal structure a cesium ion, an organic ammonium ion or an amidinium ion at each vertex of a central hexahedron; B is a lead ion; and M is one or more groups of cations selected from a valent metal element other than a cerium ion. The cation, at least a portion of M, replaces a portion of B in the aforementioned 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 ions, bromide ions, fluoride ions, iodide ions, and thiocyanate ions. One or more kinds of anions constituting the group. )

The compound having a perovskite crystal structure having A, B, X, and M as constituent components is not particularly limited, and may be a compound having a three-dimensional structure, a two-dimensional structure, or a pseudo-two-dimensional structure.

In the 3-dimensional structure, the perovskite crystal structure is represented by AB _(1-a) M _a X _(3+δ) .

In the two-dimensional structure, the perovskite crystal structure is represented by A ₂ B _(1-a) M _a X _(4+δ) .

a represents the molar ratio of M divided by the total number of M and B molar ratios [M/(M+B)].

δ is a number which can be appropriately changed in accordance with 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, δ can be selected such that the compound is neutral (charge is 0).

The basic structure of a compound having a perovskite crystal structure is usually a three-dimensional structure or a two-dimensional structure.

When the three-dimensional structure in which the composition formula based 'represents ₃ to A'B'X. 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 2-dimensional structure, the composition formula is represented by A' ₂ B'X' ₄ . Here, A', B', and X' mean the same meaning as described above.

There are three-dimensional network octahedron vertices in the above three-dimensional structure, to B 'as the center, having an apex as X' of B'X _'6 indicated.

'4 octahedron vertices X ₆ is represented in the same plane' in the above-described two-dimensional structure, to B 'as the center, by vertex X'B'X total of forming 2-dimensional connected B'X A structure in which a layer composed of ' ₆ ' and a layer formed by A' are alternately laminated.

B' is a metal cation capable of taking an 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 above-described three-dimensional structure of a compound having a perovskite crystal structure, in the X-ray diffraction pattern, a diffraction peak derived from (hkl)=(001) is usually confirmed at a position of 2θ=12 to 18°. Or at a position of 2 θ = 18 to 25°, confirm the diffraction peak from (hkl) = (100). At a position of 2 θ = 13 to 16°, confirm the diffraction peak from (hkl) = (001) or at a position of 2 θ = 20 to 23 °, and confirm the diffraction peak from (hkl) = (100) Better.

In the case of the above-described two-dimensional structure having a perovskite crystal structure, in the X-ray diffraction pattern, a diffraction peak derived from (hkl)=(002) is usually confirmed at a position of 2θ=1 to 10°. It is confirmed that the diffraction peak from (hkl) = (002) is better at a position of 2 θ = 2 to 8 °.

As a result of intensive studies by the present inventors, it has been found that in the compound having a perovskite crystal structure, the organic cation or inorganic cation of the A' component is a cerium ion, an organic ammonium ion or an amidinium ion (A). In the component), the metal cation of the B' component is a lead ion (component B), and a part of the plurality of A components and/or a component B is selected from the group consisting of cations of a monovalent metal element other than cerium ions. Substitution of the above cation (M component) improves the luminescence intensity and quantum yield.

The compound of the present invention is preferably a compound having a perovskite crystal structure represented by the following formula (1).

APb ₍₁ - _a) M _a X _(3+δ ) (0 < a ≦ 0.7, 0 ≦ δ ≦ 0.7) (1) [In the formula (1), A is a cerium ion, an organic ammonium ion or a cerium The ion, M is one or more types of cations selected from the group consisting of cations of a monovalent metal element other than cerium ions. X is one or more anions selected from the group consisting of chloride ions, bromide ions, fluoride ions, iodide ions, and thiocyanate ions. In the formula (1), a is more than 0 and not more than 0.7, and δ is 0 or more and 0.7 or less. ]

The basic structural form of perovskite is ABX ₃ , which has a three-dimensional network with vertices sharing BX ₆ octahedrons. The B component in the ABX ₃ configuration is a metal cation that can take an octahedral coordination of the X anion. The A cation is located at each vertex of a 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, it has been found that in the basic structure of the perovskite crystal structure represented by the above ABX ₃ , the metal cation of the B component is lead, and the plurality of lead is replaced by other atoms in the three-dimensional network. A part of the ions increases the luminous intensity.

In the present invention, a compound having a perovskite crystal structure represented by the formula (1) is mainly composed of lead, M and X as components A and B. Here, M means an atom which substitutes a part of lead ions of a metal cation. Further, in the above-described basic structure, M replaces the position where the B component (lead ion) exists, the position where the substitution component A exists, or the lattice gap existing in the skeleton constituting the basic structure. However, at least a part of M is preferably substituted for a part of B in the above-described perovskite crystal structure.

Hereinafter, a compound having a perovskite crystal structure in which A, B, X, and M are constituent components of the present invention will be described.

 [A]  

In the compound having a perovskite crystal structure included in the composition of the present invention, A is a cerium ion, an organic ammonium ion or a cerium ion.

In the compound having a perovskite crystal structure, when A is a cerium ion, an organic ammonium ion having 3 or less carbon atoms or a cerium ion having 3 or less carbon atoms, the perovskite crystal structure is generally AB _{( 1-a)} M _a X ₃ represents a three-dimensional structure.

The organic ammonium ion represented by A is, for example, an organic ammonium ion represented by the following formula (A1).

In the formula (A1), R ¹ to R ⁴ each independently represent a hydrogen atom, an alkyl group which may have an amine group as a substituent or a cycloalkyl group which may have an amine group as a substituent. However, R ¹ to R ^{4 are} not all hydrogen atoms.

The alkyl group represented by R ¹ to R ⁴ may be linear or branched, or may have an amine group as a substituent.

The alkyl group represented by R ¹ to R ^{4 has} usually 1 to 20 carbon atoms, preferably 1 to 4, more preferably 1 to 3 carbon atoms.

The cycloalkyl group represented by R ¹ to R ⁴ may have an amine group as a substituent.

The number of carbon atoms of the cycloalkyl group represented by R ¹ to R ⁴ is usually from 3 to 30, preferably from 3 to 11, more preferably from 3 to 8.

The base aspect 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 group and the cycloalkyl group, a perovskite crystal having a three-dimensional structure with high luminescence intensity can be obtained. Constructed compound.

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

The total number of carbon atoms contained in the alkyl group represented by R ¹ to R ^{4 is} preferably from 1 to 4, and the total number of carbon atoms contained in the cycloalkyl group represented by R ¹ to R ⁴ is 3 To 4 is better. It is more preferable that R ¹ is an alkyl group having 1 to 3 carbon atoms, and R ² to R ⁴ are a hydrogen atom.

A is CH ₃ NH ₃ ⁺ (also known as methylammonium ion), C ₂ H ₅ NH ₃ ⁺ (also known as ethylammonium ion) or C ₃ H ₇ NH ₃ ⁺ (also known as propylammonium ion) Preferably, CH ₃ NH ₃ ⁺ or C ₂ H ₅ NH ₃ ^{+ is more} preferred, and CH ₃ NH ₃ ⁺ is more preferred.

For the ruthenium ion represented by A, for example, an example of ruthenium ions represented by the following formula (A2) can be mentioned.

(R ⁵ R ⁶ N=CH-NR ⁷ R ⁸ ) ⁺ ... (A2)

In the formula (A2), R ⁵ to R ⁸ each independently represent a hydrogen atom, an alkyl group which may have an amine group as a substituent or a cycloalkyl group which may have an amine group as a substituent.

The alkyl group represented by R ⁵ to R ⁸ may be linear or branched, or may have an amine group as a substituent.

The alkyl group represented by R ⁵ to R ^{8 has} usually 1 to 20 carbon atoms, preferably 1 to 4, more preferably 1 to 3 carbon atoms.

The cycloalkyl group represented by R ⁵ to R ⁸ may have an amine group as a substituent.

The number of carbon atoms of the cycloalkyl group represented by R ⁵ to R ⁸ is usually from 3 to 30, preferably from 3 to 11, more preferably from 3 to 8.

The group represented by R ⁵ to R ⁸ is preferably a hydrogen atom or an alkyl group.

By reducing the number of alkyl groups and cycloalkyl groups contained in the general formula (A2) and reducing the number of carbon atoms of the alkyl group and the cycloalkyl group, a perovskite crystal structure having a three-dimensional structure with high luminescence intensity can be obtained. compound of.

When the number of carbon atoms of the alkyl group or the cycloalkyl group is 4 or more, a part or all of a compound having a two-dimensional and/or quasi-two-dimensional (quasi-2D) perovskite crystal structure can be obtained. Further, the total number of carbon atoms contained in the alkyl group represented by R ⁵ to R ^{8 is} preferably from 1 to 4, and the total number of carbon atoms contained in the cycloalkyl group represented by R ⁵ to R ^{8 is} preferably The number is preferably 3 to 4. In R ⁵ is alkyl having 1 to 3 carbon atoms, R ⁶ to R ⁸ is hydrogen atom are preferred.

 [M]  

M is one or more types of cations selected from the group consisting of cations of a monovalent metal element other than cerium ions.

From the viewpoint of maintaining a sufficient crystal structure or a quantum yield from the crystal structure of a compound having a perovskite crystal structure, M is preferably an alkali metal ion, 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 a perovskite crystal structure is dispersed in the medium is improved. Further, the luminescence intensity of the compound having a perovskite crystal structure is also improved.

The compound having a perovskite crystal structure may be a molar ratio obtained by dividing A, B, X, and M as constituent components, and dividing the number of moles of M by the total number of moles of M and B [M/( A compound having a perovskite crystal structure having a value of M+B)] of 0.7 or less.

In the above aspect, A represents a component of each vertex of the hexahedron centered on B, X represents a component of each vertex of the octahedron centered on B, and A is located in the perovskite crystal structure. a cesium ion, an organic ammonium ion or a cesium ion of each apex of a hexahedron centered on B; B is a lead ion; M is a sodium ion or a lithium ion; and X is located in the aforementioned perovskite crystal structure B is a component of each apex of the octahedron at the center, and is selected from one or more anions of a group consisting of chloride ions, bromide ions, fluoride ions, iodide ions, and thiocyanate ions.

Preferred embodiments and specific examples of the compound having a perovskite crystal structure are preferred from compounds having a perovskite crystal structure contained in the composition of the present invention in which M is sodium ion or lithium ion. The aspect and the specific examples are the same.

 [a]  

a represents the molar ratio [M/(B+M)] obtained by dividing the number of moles of M by the total number of moles of M and B.

From the viewpoint of maintaining a sufficient crystal light intensity or quantum yield from a crystal structure of a compound having a perovskite crystal structure, a is more than 0 and not more than 0.7. From the viewpoint of obtaining a sufficient crystal structure or a quantum yield from the crystal structure of the compound having a perovskite crystal structure, a is preferably 0.01 or more and 0.7 or less, more preferably 0.02 or more and 0.5 or less, and more preferably 0.03 or more. 0.4 or less is better.

In another aspect of the 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 ions, bromide ions, fluoride ions, iodide ions, and thiocyanate ions. Among them, chloride ions and bromide ions are preferably used.

When X contains chloride ions or bromide ions, the amount of chloride ions or bromide ions is preferably from 10 to 100%, more preferably from 30 to 100%, and from 70 to the total number of moles of X. 100% is better, and 80 to 100% is especially good.

When X contains two or more kinds of halide ions, the content of chloride ions or bromide ions is preferably 10 mol% or more based on the total number of moles of X, more preferably 30 mol% or more, and more preferably 30 mol% or more. 70% or more is better, and 80% or more is particularly good.

Among them, X is preferably a bromide ion. When X is two or more kinds of halide ions, the content of the halide ions can be appropriately selected depending on the emission wavelength.

As another aspect of the present invention, X is preferably a chloride ion and a bromide ion, and the content of the chloride ion is preferably 20 to 40 mol%, and the bromide ion content is a total molar amount of X. It is preferably 50 to 80 mol%.

As still another aspect of the present invention, X is preferably a chloride ion and a bromide ion, and a molar ratio of from 1.5 to 2.0 is represented by [bromide ion/chloride ion].

The compound having a perovskite crystal structure contained in the composition of the present invention is specific to a compound having a three-dimensional structure of a perovskite crystal structure represented by AB _(1-a) M _a X _(3+δ) For example, CH ₃ NH ₃ Pb _(1-a) Na _a Br _(3+δ) (0<a≦0.7, -0.7≦δ<0) CH ₃ NH ₃ Pb _(1-a) Li _a Br _{( 3+δ)} (0<a≦0.7, -0.7≦δ<0)CsPb ₍₁ - _a) Na _a Br _(3+δ) (0<a≦0.7, -0.7≦δ<0), CsPb _{(1 -a)} Li _a Br _(3+δ) (0<a≦0.7, -0.7≦δ<0), CH ₃ NH ₃ Pb _(1-a) Na _a Br _(3+δ-y) I _y (0 <a≦0.7, -0.7≦δ<0, 0<y<3), CH ₃ NH ₃ Pb _(1-a) Li _a Br _(3+δ-y) I _y (0<a≦0.7, -0.7 ≦δ<0,0<y<3), CH ₃ NH ₃ Pb _(1-a) Na _a Br _(3+δ-y) Cl _y (0<a≦0.7, -0.7≦δ<0,0<y<3), CH ₃ NH ₃ Pb _(1-a) Li _a Br _(3+δ-y) Cl _y (0<a≦0.7, 0≦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 _(1-a) Na _a Br _(3+δ-y) cl _y (0 <a 0.7, -0.7 ≦ δ <0,0 <y <3), etc. are preferred. However, the above (3 + δ - y) must be 0 or more.

Compounds having a perovskite crystal structure of composition of the present invention contains, a compound having a perovskite crystal structure as a 2-dimensional _{A 2 B (1-a)} M a X (4 + δ) represented by the structure Specific examples, for example, (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 (0<a≦0.7, -0.7≦δ<0.7, 0<y<4) is preferable. However, the above (4 + δ - y) must be 0 or more.

 <<Light emission spectrum>>  

A compound having a perovskite crystal structure is an illuminant that emits fluorescence in a visible light wavelength region. 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 700 nm or less. Preferably, it is preferably a phosphor having a peak value of 600 nm or less and a wavelength range of 580 nm or less and a better wavelength range.

The above upper limit and lower limit 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, a peak of fluorescence emitted is usually 480 to 700 nm, preferably 500 to 600 nm, and 520 to 580 nm. good.

When X is an iodide ion, the emission is 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, and preferably has a peak in a wavelength range of 730 nm or less. Fluorescent.

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

As another aspect of the present invention, when X in the compound having a perovskite crystal structure is iodide ion, the peak of the emitted fluorescence is usually 520 to 800 nm, preferably 530 to 750 nm, and 540 to 730 nm. good.

When X is a chloride ion, the emission is usually 300 nm or more, preferably 310 nm or more, more preferably 330 nm or more, and most preferably 600 nm or less, preferably 580 nm or less, and more preferably 550 nm or less. The peak of the fluorescent.

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

As another aspect of the present invention, when X in the compound having a perovskite crystal structure is a chloride ion, a peak of fluorescence emitted is usually 300 to 600 nm, preferably 310 to 580 nm, and 330 to 550 nm. good.

The maximum luminous intensity of the compound having a perovskite crystal structure of the present invention is obtained from the maximum intensity in the visible light wavelength region measured by a fluorophotometer and the transmittance of the excitation light measured by an ultraviolet visible light absorption photometer.

As the fluorescence photometer, for example, a fluorescence spectrophotometer RF-1500 (manufactured by Shimadzu Corporation) and a spectrofluorometer FT-6500 (manufactured by JASCO Corporation) can be used. As the ultraviolet visible light absorption photometer, for example, an ultraviolet visible light absorption photometer V-670 (manufactured by JASCO Corporation) manufactured by JASCO Corporation can be used.

In the present invention, the maximum luminescence intensity of the above compound can be corrected according to the following formula (S). In the following formula (S), Pmax is the maximum intensity in the visible light wavelength region, and Ep is the transmittance (%) of the excitation light.

Pmax/(100-Ep)×100...(S)

In one aspect of the present invention, the compound of the present invention comprising a bromide ion as an X component is a compound having a maximum luminescence intensity of 10 or more in the vicinity of a wavelength of 530 nm.

The maximum luminous intensity near the wavelength of 530 nm can be obtained by the following formula (S)-1.

[Maximum luminous intensity near wavelength 530 nm / (100-wavelength transmittance at 430 nm)] × 100 (S) -1

In the formula (S)-1, the maximum luminescence intensity in the vicinity of the wavelength 530 nm means the luminescence intensity of the peak of the highest intensity confirmed between the wavelengths of 520 and 540 nm.

The maximum luminous intensity in the vicinity of the aforementioned wavelength of 530 nm is preferably from 10 to 70, more preferably from 15 to 60.

In another aspect of the present invention, the compound of the present invention comprising a bromide ion and a chloride ion as an X component is a compound having a maximum luminescence intensity of 40 or more in the vicinity of a wavelength of 500 nm.

The maximum luminous intensity near the wavelength of 500 nm can be obtained by the following formula (S)-2.

[Maximum luminous intensity near wavelength 500 nm / (100-wavelength transmittance at 430 nm)] × 100 (S) -2

In the formula (S)-2, the maximum luminescence intensity near the wavelength of 500 nm means the luminescence intensity of the peak of the highest intensity confirmed between the wavelengths of 490 to 510 nm.

The maximum luminous intensity in the vicinity of the wavelength of 500 nm is preferably 40 to 100, more preferably 60 to 80.

In still another aspect of the present invention, the compound of the present invention comprising a bromide ion and an iodide ion as an X component is a compound having a maximum luminescence intensity of 10 or more in the vicinity of a wavelength of 540 nm.

The maximum luminous intensity near the wavelength of 540 nm can be obtained by the following formula (S)-3.

[Maximum luminous intensity near wavelength 540 nm / (100-wavelength transmittance at 430 nm)] × 100 (S) -3

In the formula (S)-3, the maximum luminescence intensity near the wavelength of 500 nm means the luminescence intensity of the peak of the highest intensity confirmed between the wavelengths of 530 to 550 nm.

The maximum luminous intensity in the vicinity of the aforementioned wavelength of 540 nm is preferably from 10 to 60, more preferably from 30 to 50.

In the present invention, the value of a is as described in the following method for calculating {a], and M and B in the synthesized compound can be measured from an inductively coupled plasma mass spectrometer (hereinafter also referred to as ICP-MS). The value calculated from the value of the number of ears.

 {a calculation method}  

The value of the molar ratio of M in the compound having a perovskite crystal structure divided by the total number of moles of M and B, the molar ratio [M/(M+B)], can be used in the composition The compound having a perovskite crystal structure is dissolved in a solvent such as nitric acid or N,N-dimethylformamide, and then measured.

Specifically, the value of the molar ratio [M/(M+B)] is a value calculated from the following formula (T). In the following formula (T), Mmol is the number of moles of M measured by ICP-MS, and Pbmol represents the number of moles of Pb measured by ICP-MS.

[M/(M+B)]=(Mmol)/(Mmol+Pbmol)...(T)

In the present invention, from the viewpoint of more accurately calculating the substitution amount of M to Pb in the compound after synthesis, the value calculated by the calculation method of {a is preferably "a".

Further, the value of a can be simply calculated from the value adjusted so that the a of the compound of the present invention becomes a feed ratio of a desired value when synthesizing the compound of the present invention.

 <dispersion composition>  

In the dispersion composition of the present invention, the medium of the above composition is a liquid composition, and the compound having a perovskite crystal structure is dispersed in a liquid. By making the above-described compound having a perovskite crystal structure into a dispersion composition, the quantum yield can be improved.

In the present specification, the term "liquid" means a substance that is in a liquid state at 1 atm and at 25 °C.

The dispersion composition may include the above-described compound having a perovskite crystal structure and other components than the liquid. As the above-mentioned components, for example, an impurity, A, B, X, and/or M as a constituent component of a compound having an amorphous structure and a terminal ligand are contained.

As the impurity, for example, a halide containing A, B and/or M; an oxide of B and/or M, a composite oxide; and other compounds containing A, B, X and/or M. The other component is preferably 10% by mass or less based on the total mass of the dispersion composition.

The liquid (excluding the resin) contained in the dispersion composition is not particularly limited as long as it is a liquid which can disperse the above compound having a perovskite crystal structure.

The liquid contained in the dispersion composition (except for the resin) is preferably one which does not easily dissolve the above compound having a perovskite crystal structure.

As the liquid contained in the composition of the dispersion (except for the resin), for example, esters of methyl formate, ethyl formate, propyl formate, amyl formate, methyl acetate, ethyl acetate, amyl acetate, etc.; a ketone such as butyrolactone, N-methyl-2-pyrrolidone, acetone, dimethyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone or methylcyclohexanone; diethyl ether, Methyl 3 butyl ether, diisopropyl ether, dimethoxy methane, dimethoxy ethane, 1,4-two An ether of alkane, 1,3-dioxolane, 4-methyldioxolane, tetrahydrofuran, methyltetrahydrofuran, anisole, phenethyl ether, etc.; methanol, ethanol, 1-propanol, 2-propanol , 1-butanol, 2-butanol, third butanol, 1-pentanol, 2-methyl-2-butanol, methoxypropanol, diacetone alcohol, cyclohexanol, 2-fluoroethanol, Alcohols such as 2,2,2-trifluoroethanol, 2,2,3,3-tetrafluoro-1-propanol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, Glycol ether of ethylene glycol monoethyl ether acetate, triethylene glycol dimethyl ether, etc.; N,N-dimethylformamide, acetamide, NN-dimethylacetamide, etc. Organic solvent having a nitrile group; an organic solvent having a nitrile group such as acetonitrile, isobutyronitrile, propionitrile or methoxyacetonitrile; an organic solvent having a hydrocarbon group such as ethyl carbonate or propyl carbonate; methyl chloride and dichloromethane An organic solvent having a halogenated hydrocarbon group such as chloroform; an organic solvent having a hydrocarbon group such as n-pentane, cyclohexane, n-hexane, benzene, toluene or xylene; dimethyl hydrazine or the like.

Among these organic solvents, esters of methyl formate, ethyl formate, propyl formate, amyl formate, methyl acetate, ethyl acetate, amyl acetate, etc.; γ-butyrolactone, acetone, dimethyl Ketones such as ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methylcyclohexanone; diethyl ether, methyl butyl ether, diisopropyl ether, dimethoxymethane, two Methoxyethane, 1,4-two Ethers of alkane, 1,3-dioxolane, 4-methyldioxolane, tetrahydrofuran, methyltetrahydrofuran, anisole, phenylethyl ether, etc.; acetonitrile, isobutyronitrile, propionitrile, methoxyacetonitrile An organic solvent having a nitrile group; an organic solvent having a carbonate group such as ethyl carbonate or propyl carbonate; an organic solvent having a halogenated hydrocarbon group such as methyl chloride, dichloromethane or chloroform; An organic solvent having a hydrocarbon group such as alkane, cyclohexane, n-hexane, benzene, toluene or xylene is considered to be a compound having a low polarity and hardly soluble in a perovskite crystal structure, and thus it is preferred to use methyl chloride. An organic solvent having a halogenated hydrocarbon group such as dichloromethane or chloroform; a hydrocarbon-based organic solvent such as n-pentane, cyclohexane, n-hexane, benzene, toluene or xylene is more preferable.

The dispersion composition of the present invention may comprise a capping ligand. The capped ligand is a surface which is adsorbed on a surface of a particle (a compound having a perovskite crystal structure), and a compound which is stably dispersed in a dispersion solvent is, for example, a terminal ligand (A3) An ammonium salt represented by the formula and a compound having a carboxyl group represented by (A4). The dispersion composition of the present invention may comprise either an ammonium salt represented by the formula (A3) or a compound having a carboxyl group represented by the formula (A4), or both.

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

In the formula (A3), R ⁹ to R ¹² each independently represent a hydrogen atom, an alkyl group which may have an amine group as a substituent, an unsaturated hydrocarbon group which may have one amino group as a substituent or may have an amine group as a substituent. a cycloalkyl group.

The alkyl group represented by R ⁹ to R ¹² may be linear or branched, or may have an amine group as a substituent.

The alkyl group represented by R ⁹ to R ^{12 has} usually 1 to 20 carbon atoms, preferably 5 to 20, more preferably 8 to 20 carbon atoms.

The unsaturated hydrocarbon group represented by R ⁹ to R ¹² may be linear or branched, or may have one amine group as a substituent. The number of carbon atoms of the unsaturated hydrocarbon group represented by R ⁹ to R ¹² is usually 2 to 20, preferably 5 to 20, more preferably 8 to 20.

The cycloalkyl group represented by R ⁹ to R ¹² may have an amine group as a substituent.

The number of carbon atoms of the cycloalkyl group represented by R ⁹ to R ¹² is usually from 3 to 30, preferably from 3 to 20, more preferably from 3 to 11.

R ⁹ to R ¹² are hydrogen atoms based, preferably an alkyl group or unsaturated hydrocarbon group. As the unsaturated hydrocarbon group, an alkenyl group is preferred.

The ammonium salt represented by the formula (A3) may be adsorbed on the surface of the compound having a perovskite crystal structure or may be dispersed in a solvent. The relative anion of the above ammonium salt is not particularly limited, and examples thereof include halide ions of Br ^- , Cl ^- , I ^- , and F ^- .

The ammonium salt represented by the formula (A3) is preferably a salt of n-octylamine or a salt of oleylamine.

The dispersion composition may contain a compound having a carboxyl group represented by (A4).

R ¹³ -CO ₂ H...(A4)

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

The alkyl group represented by R ¹³ may be linear or branched, or may have one carboxyl group as a substituent. The alkyl group represented by R ^{13 has} usually 1 to 20 carbon atoms, preferably 5 to 20, more preferably 8 to 20 carbon atoms.

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

The cycloalkyl group represented by R ¹³ may have one carboxyl group as a substituent.

The cycloalkyl group represented by R ^{13 has} usually 3 to 30 carbon atoms, preferably 3 to 20, 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 preferred.

The compound having a carboxyl group represented by (A4) may be adsorbed on the surface of the compound having a perovskite crystal structure or may be dispersed in a solvent.

As the compound having a carboxyl group represented by (A4), oleic acid is preferred.

The content of the compound having a perovskite crystal structure contained in the dispersion composition is not particularly limited, and from the viewpoint of preventing aggregation of a compound having a perovskite crystal structure and preventing concentration quenching, The total mass of the dispersion composition is preferably 50% by mass or less, more preferably 10% by mass or less, and more preferably 1 ppm by mass or more from the viewpoint of obtaining a sufficient quantum yield. More than ppm by mass.

In another aspect of the present invention, the content of the compound having a perovskite crystal structure contained in the dispersion composition is 1 ppm by mass or more and 50% by mass or less based on the total mass of the dispersion composition. Preferably, it is more preferably 10 mass ppm or more and 10 mass% or less.

In the present specification, the content of the compound having a perovskite crystal structure is, for example, by ICP-MS or inductively coupled plasma luminescence spectrometry (hereinafter also referred to as ICP-) for the total mass of the dispersion composition. AES), ion chromatography, or the like can be measured by analyzing an element constituting the perovskite crystal structure, and can be calculated from a molar ratio by measuring a part of an element constituting the perovskite crystal structure. Determination.

The average particle diameter of the compound having a perovskite crystal structure dispersed in the dispersion composition is not particularly limited, and from the viewpoint of sufficiently maintaining the crystal structure, the average particle diameter is preferably 1 nm or more, and more preferably 2 nm or more. Preferably, it is more preferably 3 nm or more, and from the viewpoint of preventing the compound having a perovskite crystal structure from being easily precipitated, the average particle diameter is preferably 10 μm or less, more preferably 1 μm or less, and still more preferably 500 nm or less.

As a further aspect of the present invention, the average particle diameter of the aforementioned compound having a perovskite crystal structure dispersed in the dispersion composition is preferably from 1 nm to 10 μm, more preferably from 2 nm to 1 μm, still more preferably from 3 nm to 500 nm. .

In the present specification, the average particle diameter of the compound having a perovskite crystal structure dispersed in the dispersion composition can be, for example, a scanning electron microscope (hereinafter also referred to as SEM) or a transmission electron microscope (hereinafter). Also known as TEM) determination. Specifically, the particle size of 20 of the above-described compounds having a perovskite crystal structure dispersed in the dispersion composition can be observed by TEM or SEM, and the average value can be calculated by calculating the average value of the above-mentioned dispersion composition. The aforementioned average particle diameter.

The particle size distribution of the compound having a perovskite crystal structure contained in the dispersion composition is not particularly limited, and from the viewpoint of sufficiently maintaining the crystal structure, the median diameter D50 is preferably 3 nm or more. More preferably, it is 4 nm or more, more preferably 5 nm or more, and from the viewpoint that the compound having a perovskite crystal structure is less likely to settle, it is preferably 5 μm or less, more preferably 500 nm or less, and still more preferably 100 nm or less.

In another aspect of the invention, the particle size distribution of the compound having a perovskite crystal structure contained in the dispersion composition is preferably 3 nm to 5 μm, more preferably 4 nm to 500 nm. More preferably from 5 nm to 100 nm.

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 size of 20 of the above-described compounds having a perovskite crystal structure dispersed in the dispersion composition is observed by TEM or SEM, and the median diameter can be obtained from the distributions. D50.

 <<calculation of a>>  

In the dispersion composition of the present invention, the molar ratio [M/(M+B)] obtained by dividing the number of moles of M described above by the total number of moles of M and B can be used for ICP-MS (ELAN) Measured by DRCII, manufactured by Perkin Elmer. The compound having a perovskite crystal structure in the dispersion composition can be measured by dissolving in a solvent such as nitric acid or N,N-dimethylformamide.

The specific calculation method is the same as the method for calculating the compound having the perovskite crystal structure.

 <<Measurement of quantum yield>>  

The quantum yield of the dispersion composition of the present invention can be measured using an absolute PL quantum yield measuring device (manufactured by Hamamatsu Photonics Co., Ltd., trade name C9920-02, measurement conditions: excitation light 450 nm, room temperature, atmospheric pressure). The quantum yield of the dispersion composition is measured by adjusting the compound having a perovskite crystal structure to a concentration of 100 to 2000 ppm (μg/g) based on the total mass of the dispersion composition.

One aspect of the present invention includes a composition of a compound of the present invention containing an organic ammonium ion as the component A, and a composition having a quantum yield of 80% or more as measured by the above method.

As the aforementioned quantum yield, it is preferably 80 to 100%, more preferably 85 to 100%.

Another aspect of the present invention includes a composition of the compound of the present invention containing cerium ions as the component A, and a composition having a quantum yield of 40% or more as measured by the above method.

As the aforementioned quantum yield, it is preferably 40 to 100%, more preferably 40 to 80%.

 <Resin composition>  

In the resin composition of the present invention, the medium in the above composition is a resin composition, and the compound having a perovskite crystal structure is dispersed in the resin. By making the above compound having a perovskite crystal structure into a resin composition, the quantum yield can be improved.

In the present specification, the term "resin" means an organic polymer compound.

The resin composition may contain the above-described compound having a perovskite crystal structure and other components than the resin. The other components are the same as the other components which can be contained in the above-described dispersion composition of the present invention. The other component is preferably 10% by mass or less based on the total mass of the dispersion composition.

The form of the resin composition of the present invention is not particularly limited and may be appropriately determined depending on the use. The resin composition in which the compound having a perovskite crystal structure is dispersed may be in the form of a film or may be formed into a plate shape.

In the resin composition of the present invention, the resin having a perovskite crystal structure is not particularly limited, but is a compound having a perovskite crystal structure at a temperature at which the resin composition is produced. Those with low solubility are preferred.

Examples of the resin include polystyrene, methacrylic resin, and the like.

The amount of the compound having a perovskite crystal structure contained in the resin composition is not particularly limited, and from the viewpoint of preventing aggregation of a compound having a perovskite crystal structure and preventing concentration quenching, the resin is The total mass of the composition is preferably 50% by mass or less, more preferably 10% by mass or less, and more preferably 1 ppm by mass or more, and 10 ppm by mass or more from the viewpoint of obtaining sufficient quantum yield. Better.

In another aspect of the invention, the content of the compound having a perovskite crystal structure contained in the resin composition is preferably 1 ppm by mass or more and 50% by mass or less based on the total mass of the resin composition. It is more preferably 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 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, and is the same as the average particle diameter of the compound having a perovskite crystal structure dispersed in the dispersion composition.

The particle size distribution of the compound having a perovskite crystal structure contained in the resin composition is not particularly limited, and is the same as the particle size distribution of the compound having a perovskite crystal structure dispersed in the dispersion composition. .

 <<calculation of a>>  

In the resin composition of the present invention, the molar ratio [M/(M+B)] obtained by dividing the number of moles of M by the total number of moles of M and B is the dispersion of the present invention. The composition was the same and can be measured using ICP-MS (ELAN DRCII, manufactured by Perkin Elmer).

 <<Measurement of quantum yield>>  

The quantum yield of the resin composition of the present invention is the same as that of the dispersion composition of the present invention, and an absolute PL quantum yield measuring device (manufactured by Hamamatsu Photonics Co., Ltd., trade name C9920-02, measurement conditions: excitation light) can be used. The measurement was carried out at 450 nm, room temperature, and atmosphere.

 <Method for Producing 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 containing Pb and the above X compound, a compound containing the above M and the above X, and a compound containing the above A and the above X dissolved in a solvent are applied to a substrate, and the solvent is used to synthesize the calcium and titanium of the present invention. A compound of a mineral crystal structure.

In another method, a solution containing Pb and the above X compound and a compound containing the above M and the above X dissolved in a solvent is applied to a substrate, and a solvent is removed to form a coating film, and the compound containing the above A and the above X is used. The solution dissolved in the solvent is applied onto the above-mentioned coating film, and the compound having a perovskite crystal structure of the present invention can be synthesized by removing the solvent.

In the synthesis, a and δ may be set to a desired value, and the type and amount of the compound to be blended may be adjusted.

Examples of the coating method include a gravure coating method, a bar coating method, a printing method, a spray coating method, a spin coating method, a dipping method, and a slit coating method.

Examples of the method for removing the solvent include decomposing one or more of reduced pressure, drying, and blowing, and volatilizing the solvent. Drying can be carried out at room temperature or by heating. The temperature at the time of heating can be appropriately determined in consideration of the time required for drying and the heat resistance of the substrate, preferably 50 to 200 ° C, more preferably 50 to 100 ° C.

The solvent to be used in the method for producing the compound is not particularly limited as long as it can dissolve the above-mentioned A, B, M, X and other components, and is, for example, the same as the liquid (excluding the resin) contained in the dispersion composition. .

Among them, from the viewpoint of easily ensuring the solubility of the above-mentioned A, B, M, X and other components, N-methyl-2-pyrrolidone, N,N-dimethylformamide, acetamide, An organic solvent having a guanamine group such as N,N-dimethylacetamide or the like, dimethyl hydrazine is suitable, and N,N-dimethylformamide is more suitable.

The organic solvent may have a branched structure or a cyclic structure, and may have a plurality of functional groups such as -O-, -CO, -COO-, -OH, etc., and the hydrogen atom may be substituted by a halogen atom such as fluorine.

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, more preferably 90% by mass or more, based on the total mass of the solution.

 <Method for Producing Dispersion Composition>  

The dispersion composition of the present invention can be produced by the method described below with reference to a known document (Nano Lett. 2015, 15, 3692-3696, ACS Nano, 2015, 9, 4533-4542, etc.).

For example, the method for producing a dispersion composition of the present invention includes, for example, a production method comprising a compound containing B and X components, a compound containing M component and X, and a compound containing A or A and X. a step of dissolving a compound in a solvent to obtain a solution; and a step of mixing the obtained solution with a solvent having a lower solubility than a solvent used in the step of obtaining a solution having a perovskite crystal structure (dispersion composition) The first embodiment of the method).

Further, for example, a production method comprising the steps of: 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 solvent having a high temperature, and dissolving the solution to obtain a solution And a step of cooling the obtained solution (the second embodiment of the dispersion composition).

 <First embodiment of dispersion composition>  

Hereinafter, the following production method will be described. The production method includes the steps of dissolving a compound containing B and X, a compound containing M and X, and a compound containing A or a compound containing A and X in a solvent. a step of solution; and a step of mixing the obtained solution with a solvent having a lower solubility than a solvent used in the step of obtaining a solution for a compound having a perovskite crystal structure.

In addition, the solubility means the solubility of the temperature at which the mixing step is performed.

In the above production method, from the viewpoint of stably dispersing a compound having a perovskite crystal structure, it is preferred to include a step of adding a capping ligand. The terminal ligand is preferably added before the aforementioned mixing step, and the solubility ratio of the terminal ligand added to the solution of the dissolved A, B, X and M is added to the compound having a perovskite crystal structure. The step of obtaining a solution is added to a solvent having a low solvent, or may be used in a step of obtaining a solution by dissolving a solution of A, B, X, and M and a solubility ratio of a compound having a perovskite crystal structure. It is added to both solvents with low solvent.

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

The step of mixing the solution with a solvent having a lower solubility than the solvent used in the step of obtaining the solution for the perovskite crystal structure may be (a) dropping the solution into the pair having a perovskite type. a step in which the solubility of the compound of the crystal structure is lower than the solvent used in the step of obtaining the solution, or (b) the solubility ratio of the compound having a perovskite crystal structure to the solution obtained in the solution The step of using a solvent having a low solvent for the step is preferably (a) from the viewpoint of improving dispersibility.

It is preferable to carry out stirring at the time of dropping, from the viewpoint of improving dispersibility.

In the step of mixing the solution with a solvent having a lower solubility than the solvent used in the step of obtaining the solution of the perovskite type, the temperature is not particularly limited, but from ensuring a perovskite crystal structure. From the viewpoint of easiness of precipitation of the compound, it is preferably in the range of 0 to 40 ° C, more preferably in the range of 10 to 30 ° C.

At the time of production, the type and amount of the compound to be blended can be adjusted so that a and δ become desired values.

The two solvents having different solubility in the compound having a perovskite crystal structure used in the above production method are not particularly limited, and are, for example, selected from the group consisting of methanol, ethanol, 1-propanol, 2-propanol, and 1- Butanol, 2-butanol, third butanol, 1-pentanol, 2-methyl-2-butanol, methoxypropanol, diacetone alcohol, cyclohexanol, 2-fluoroethanol, 2,2 An alcohol such as 2-trifluoroethanol or 2,2,3,3-tetrafluoro-1-propanol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol a glycol ether such as monoethyl ether acetate or triethylene glycol dimethyl ether; or an organic amine having a guanamine group such as N,N-dimethylformamide, acetamide or NN-dimethylacetamide Solvent; esters of dimethyl hydrazine, methyl formate, ethyl formate, propyl formate, amyl formate, methyl acetate, ethyl acetate, amyl acetate; γ-butyrolactone, N-methyl Ketones such as 2-pyrrolidone, acetone, dimethyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methylcyclohexanone; diethyl ether, methyl 3 butyl ether, two Isopropyl ether, dimethoxymethane, dimethoxyethane, 1,4-two Ethers of alkane, 1,3-dioxolane, 4-methyldioxolane, tetrahydrofuran, methyltetrahydrofuran, anisole, phenylethyl ether, etc.; acetonitrile, isobutyronitrile, propionitrile, methoxyacetonitrile An organic solvent having a nitrile group; an organic solvent having a carbonate group such as ethyl carbonate or propyl carbonate; an organic solvent having a halogenated hydrocarbon group such as methyl chloride, dichloromethane or chloroform; Two solvents of a group consisting of an organic solvent having a hydrocarbon group such as alkane, cyclohexane, n-hexane, benzene, toluene or xylene.

The solvent used in the step of obtaining the solution obtained in the above production method is preferably a solvent having a high solubility to a compound having a perovskite crystal structure, for example, when the above steps are carried out at room temperature (10 ° C to 30 ° C). For example, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, third butanol, 1-pentanol, 2-methyl-2-butanol, methoxypropyl Alcohols such as alcohol, diacetone alcohol, cyclohexanol, 2-fluoroethanol, 2,2,2-trifluoroethanol, 2,2,3,3-tetrafluoro-1-propanol; a glycol ether of ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, triethylene glycol dimethyl ether, etc.; N,N-dimethylformamide, acetamidine An organic solvent having a guanamine group such as an amine or NN-dimethylacetamide; dimethyl hydrazine.

The solvent to be used in the mixing step of the above-described production method is preferably a solvent having a low solubility to a compound having a perovskite crystal structure, for example, when the above steps are carried out at room temperature (10 ° C to 30 ° C), for example Esters of methyl formate, ethyl formate, propyl formate, amyl formate, methyl acetate, ethyl acetate, amyl acetate; γ-butyrolactone, N-methyl-2-pyrrolidone, acetone , ketones such as dimethyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methylcyclohexanone; diethyl ether, methyl 3 butyl ether, diisopropyl ether, dimethoxy Methane, dimethoxyethane, 1,4-two Ethers of alkane, 1,3-dioxolane, 4-methyldioxolane, tetrahydrofuran, methyltetrahydrofuran, anisole, phenylethyl ether, etc.; acetonitrile, isobutyronitrile, propionitrile, methoxyacetonitrile An organic solvent having a nitrile group; an organic solvent having a carbonate group such as ethyl carbonate or propyl carbonate; an organic solvent having a halogenated hydrocarbon group such as methyl chloride, dichloromethane or chloroform; An organic solvent having a hydrocarbon group such as an alkane, cyclohexane, n-hexane, benzene, toluene or xylene.

Among the two solvents having different solubility, the difference in solubility is preferably 100 μg / solvent 100 g to 90 g / solvent 100 g, more preferably 1 mg / solvent 100 g to 90 g / solvent 100 g. From the viewpoint of a difference in solubility of 100 μg / solvent 100 g to 90 g / solvent 100 g, for example, when the mixing step is carried out at room temperature (10 ° C to 30 ° C), the solvent used in the step of obtaining a solution is NN-dimethylacetamide Or an organic solvent having a guanamine group or dimethyl hydrazine, and the solvent used in the mixing step is an organic solvent having a halogenated hydrocarbon group such as methyl chloride, dichloromethane or chloroform; n-pentane or cyclohexane. An organic solvent having a hydrocarbon group such as n-hexane, benzene, toluene or xylene is preferred.

 <Second embodiment of the method for producing a dispersion composition>  

Hereinafter, a production method including the following steps will be described: a compound containing B and X, a compound containing M and X, a compound containing A or a compound containing A and X are added to a solvent having a high temperature and dissolved. a step of the solution; and a step of cooling the resulting solution.

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

In the above production method, from the viewpoint of stably dispersing the perovskite compound, it is preferred to include a step of adding a capping ligand.

In the above production method, after the cooling step, a step of removing coarse particles by a method such as centrifugation, filtration or the like is preferred. The size of the coarse particles removed by the above 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 which dissolves a compound containing B and X and a compound containing A or a compound containing A and X. For example, a solvent of 60 to 600 ° C is preferably used, and 80 to The solvent at 400 ° C is more preferable.

As the cooling temperature, it is preferably from -20 to 50 ° C, more preferably from -10 to 30 ° C.

As the cooling rate, it is preferably from 0.1 to 1500 ° C / min, more preferably from 10 to 150 ° C / min.

The solvent to be used in the above production method is not particularly limited as long as it is a solvent capable of dissolving a compound containing B and X, a compound containing M and X, a compound containing the component A, or a compound containing the component A and the component X. It is the same as the liquid (except the resin) contained in the above dispersion composition.

As a method of taking out a perovskite compound from a dispersion containing a perovskite compound, for example, a method of recovering only a perovskite compound by solid-liquid separation.

The method of solid-liquid separation described above is, for example, a method such as filtration, a method using evaporation of a solvent, or the like.

 <Method for Producing Resin Composition>  

For example, the method for producing the resin composition of the present invention includes a method of producing a compound having a perovskite crystal structure or a dispersion composition of the present invention and a solution in which a resin is dissolved in a solvent. a step of mixing; and a step of removing the solvent.

Further, a production method comprising the steps of: mixing the compound having a perovskite crystal structure or the dispersion composition of the present invention with a monomer; and polymerizing the monomer to obtain a resin composition may be mentioned. A step of.

Hereinafter, a method for producing a resin composition comprising the following steps: a step of mixing the compound having a perovskite crystal structure or the dispersion composition of the present invention with a solution in which a resin is dissolved in a solvent; and removing The step of the solvent.

In the mixing step of the above compound having a perovskite crystal structure or the dispersion composition of the present invention and a solution in which the resin is dissolved in a solvent, (a) the above compound having a perovskite crystal structure or the present invention may be used. The step of dropping the dispersion composition into the solution in which the resin is dissolved in the solvent may be (b) dropping the solution in which the resin is dissolved in the solvent into the above-mentioned compound having a perovskite crystal structure or the dispersion composition of the present invention. From the viewpoint of improving dispersibility, (a) is preferred.

It is preferable to carry out stirring at the time of mixing, from the viewpoint of improving dispersibility.

In the mixing step of the perovskite compound or the dispersion composition of the present invention and the resin dissolved in the solvent, the temperature is not particularly limited, and from the viewpoint of uniform mixing, it is preferably in the range of 0 to 100 ° C, and 10 to 80 ° C. The scope is better.

The method for removing the solvent may be, for example, natural drying by standing at room temperature, and may be a method of drying under reduced pressure using a vacuum dryer or evaporating a solvent by heating.

The solvent for dissolving the resin is not particularly limited as long as it is a solvent capable of dissolving the resin, but it is preferred that the perovskite compound is not easily dissolved.

The solvent for dissolving the resin is, for example, the same as the liquid (excluding the resin) contained in the dispersion composition described above.

Among them, esters of methyl formate, ethyl formate, propyl formate, amyl formate, methyl acetate, ethyl acetate, amyl acetate, etc.; γ-butyrolactone, acetone, dimethyl ketone, diiso Ketones such as butyl ketone, cyclopentanone, cyclohexanone, methylcyclohexanone; diethyl ether, methyl tertiary butyl ether, diisopropyl ether, dimethoxymethane, dimethoxyethane 1,4-two Ethers of alkane, 1,3-dioxolane, 4-methyldioxolane, tetrahydrofuran, methyltetrahydrofuran, anisole, phenylethyl ether, etc.; acetonitrile, isobutyronitrile, propionitrile, methoxyacetonitrile Or an organic solvent having a nitrile group; a carbonate-based organic solvent such as ethyl carbonate or propylene carbonate; an organic solvent having a halogenated hydrocarbon group such as methyl chloride, dichloromethane or chloroform; An organic solvent having a hydrocarbon group such as alkane, cyclohexane, n-hexane, benzene, toluene or xylene is considered to be low in polarity and hardly soluble in a perovskite compound, and is preferably methyl chloride or dichloromethane. An organic solvent having a halogenated hydrocarbon group such as chloroform; an organic solvent having a hydrocarbon group such as n-pentane, cyclohexane, n-hexane, benzene, toluene or xylene is more preferable.

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

The step of mixing the compound having a perovskite crystal structure or the dispersion composition of the present invention with a monomer may be (a) dropping the above compound having a perovskite crystal structure or the dispersion composition of the present invention The monomer may be (b) the monomer may be dropped into the above-described compound having a perovskite crystal structure or the dispersion composition of the present invention, and (a) is preferred from the viewpoint of improving dispersibility.

From the viewpoint of improving dispersibility, it is preferred to carry out the stirring while mixing.

In the step of mixing the above perovskite compound or the dispersion composition of the present invention with a monomer, the temperature is not particularly limited, but from the viewpoint of uniform mixing, it is preferably in the range of 0 to 100 ° C, and 10 to 80. The range of °C is better.

As the monomer used in the above production method, for example, styrene or methyl methacrylate.

In the above production method, as a method of polymerizing a monomer, a conventional polymerization reaction such as radical polymerization can be suitably used. For example, in the case of radical polymerization, a radical polymerization initiator is added to a compound having a perovskite crystal structure or a mixture of the dispersion composition of the present invention and a monomer, and a polymerization reaction by generating a radical is used. A radical is generated and a polymerization reaction is carried out.

The radical polymerization initiator is not particularly limited, and is, for example, a photoradical polymerization initiator.

The photoradical polymerization initiator is, for example, bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide.

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

 <film>  

The film of the present invention is a film comprising the above-described resin composition of the present invention or a film comprising the above-described compound having a perovskite crystal structure of the present invention.

The thickness of the film of the present invention is usually from 0.01 μm to 10 mm, preferably from 0.1 μm to 1 mm, more preferably from 1 μm to 0.5 mm.

In the present specification, the thickness of the film can be measured at any three points by a micrometer and calculated by calculating the average value.

The film of the present invention may contain a single compound having a perovskite crystal structure, or may contain two or more kinds.

 <Method for Producing Film>  

The film of 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 of the present invention described above.

As another method of the method for producing a film of the present invention, for example, a coating method using a dispersion composition in the present invention can be mentioned.

Here, the dispersion composition of the compound having a perovskite crystal structure of the present invention is the same as the dispersion composition of the present invention described above. The dispersion composition may be the above composition comprising the resin composition of the present invention.

As an aspect of the coating method using the dispersion composition, for example, a method of coating a dispersion composition on a substrate and removing the solvent to produce the film of the present invention is used.

As another aspect of the coating method using the dispersion composition, for example, a dispersion composition further containing a monomer is applied onto a substrate, and the film of the present invention is produced by polymerizing the monomer by removing the solvent.

 <Laminated structure>  

The laminated structure of the present invention is a laminated structure having a layer including the above-described resin composition of the present invention or a laminated structure having a layer containing the compound of the present invention having a perovskite crystal structure.

The layer containing the resin composition of the present invention and the layer containing the compound having a perovskite crystal structure of the present invention have a thickness of usually 0.01 μm to 10 mm, preferably 0.1 μm to 1 mm, and 1 μm to 0.5 mm. good.

In the present specification, the thickness of the film can be measured at any three points by a micrometer and calculated by calculating the average value.

The laminated structure of the present invention may have only one layer of a layer containing the resin composition of the present invention, or may have two or more layers; and may have only one layer of a layer containing a compound having a perovskite crystal structure of the present invention. It can also have more than two layers.

The layered structure of the present invention may include a layer containing the resin composition of the present invention or a layer other than the layer containing the compound having a perovskite crystal structure of the present invention, and examples thereof include a substrate, a barrier layer, a light scattering layer, and the like. .

 (substrate)  

The substrate is not particularly limited, and a transparent substrate is preferred from the viewpoint of taking out light emitted. The substrate is, for example, a flexible substrate made of polyethylene terephthalate or the like, or a glass substrate.

 (barrier layer)  

The barrier layer refers to a layer having a function of protecting a layer containing the resin composition of the present invention or a layer containing a compound having a perovskite crystal structure of the present invention to avoid water vapor or the like in the atmosphere.

The barrier layer is not particularly limited, and a transparent layer is preferred from the viewpoint of taking out light emitted. As the barrier layer, a conventional barrier layer such as a SiO ₂ film, an Al ₂ O ₃ film or the like can be used.

 (light scattering layer)  

The light scattering layer is a layer having a function of scattering light that emits light.

The light-scattering layer is not particularly limited, and a transparent layer is preferred from the viewpoint of taking out light emitted. As the light-scattering layer, for example, a layer containing light-scattering particles such as cerium oxide particles or an enlarged diffusion film.

Fig. 1 is a schematic cross-sectional view showing the configuration of a laminated structure of the present embodiment. The first laminated structure 1a is provided between the first substrate 20 and the second substrate 21, and is provided with a layer 10 containing the resin composition of the present invention or the compound having a perovskite crystal structure of the present invention. Moreover, the aforementioned layer 10 is sealed by the sealing layer 22.

One aspect of the present invention includes a first substrate 20, a second substrate 21, and a layer 10 including a compound having a perovskite crystal structure of the present invention and a seal between the first substrate 20 and the second substrate 21. The laminated structure of the layer is characterized in that the sealing layer is disposed on a surface of the layer 10 including the compound having a perovskite crystal structure and not in contact with the first substrate 20 and the second substrate 21 1a.

According to another aspect of the present invention, the slab 50, the light guide plate 60, and the laminated structure 1b of the first laminated structure 1a are sequentially laminated.

 <Method of Manufacturing Multilayer Structure>  

The layer containing the resin composition of the present invention and the method for producing the layer containing the compound having a perovskite crystal structure of the present invention are the same as those of the film of the present invention. Therefore, the laminated structure of the present invention can be produced by combining the above-described method for producing a film of the present invention and a conventional method.

 <Lighting device>  

The light-emitting device of the present invention is a light-emitting device comprising the laminated structure of the present invention and a light source. When the light emitted from the light source is irradiated onto the laminated structure, it is absorbed by a layer containing a resin composition or a compound having a perovskite crystal structure, and includes a resin composition or a layer luminescence of a compound having a perovskite crystal structure. A device for taking out emitted light from a layer containing a resin composition or a compound having a perovskite crystal structure. In the light-emitting device of the present invention, a layer containing a resin composition or a compound having a perovskite crystal structure generally functions as a wavelength-converting light-emitting layer.

In one aspect of the invention, the enamel sheet 50, the light guide plate 60, the first laminated structure 1a, and the light source device 2 of the light source 30 are sequentially laminated.

In the light-emitting device of the present invention, the layer other than the above which may be included in the laminated structure of the present invention is, for example, a light-reflecting member layer, a brightness-enhancing layer, a sheet, a light guide plate, and a dielectric material layer between the constituent elements.

 (light source)  

The light source is not particularly limited, and a light source having an emission wavelength of 600 nm or less is preferable from the viewpoint of light-emitting of a layer containing a resin composition or a compound having a perovskite crystal structure in the laminated structure. As the light source, for example, a light-emitting diode (LED) such as a blue light-emitting diode, a laser, or an EL (electrically-excited light).

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

As another specific example of the light-emitting device of the present invention, for example, illumination. The blue light-emitting diode is used as a light source, and a layer containing a resin composition or a compound having a perovskite crystal structure as a function of a wavelength-converting light-emitting layer can realize illumination of white light.

 <liquid crystal display>  

As shown in FIG. 2, the liquid crystal display 3 of the present embodiment includes the 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 a second laminated structure 1b and a light source 30. In the second laminated structure 1b, the first laminated structure 1a further includes a cymbal 50 and a light guide plate 60. The display can have any other suitable components.

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

 <Use>  

Examples of the use of the compound having a perovskite crystal structure and the dispersion composition and the resin composition of the present invention include, for example, an EL display and a wavelength conversion material for a liquid crystal display. Specifically, (1) The compound having a perovskite crystal structure of the present invention is placed in a glass tube and sealed, and disposed along the end surface (side surface) of the light guide plate between the blue light-emitting diode of the light source and the light guide plate, (2) A compound having a perovskite crystal structure of the present invention is dispersed in a resin or the like to be thinned, and the film is sealed by two sheets of a barrier film. The film is disposed on the light guide plate, and the blue light emitting diode placed on the end surface (side surface) of the light guide plate passes through the light guide plate, and the blue light irradiated to the front sheet is converted into a backlight of green light and red light (surface mount type (3) The compound having a perovskite crystal structure of the present invention is dispersed in a resin or the like, and is disposed in the vicinity of the light-emitting portion of the blue light-emitting diode, and the irradiated blue light is converted into green light and red. Light from a backlight (backlight wafer mode); and (4) a compound having a perovskite crystal structure according to the present invention are dispersed in photoresists. It is disposed on the color filter, and the blue light irradiated from the light source is converted into a backlight of green light and red light.

The use of the composition containing the compound having a perovskite crystal structure of the present invention may, for example, be a wavelength conversion material for a laser diode. Specifically, a composition comprising a compound having a perovskite crystal structure of the present invention is formed, and is disposed in a subsequent stage of a blue light-emitting diode of a light source, and converts blue light into green light and red light. White light illumination.

Further, the compound having a perovskite crystal structure of the present invention can be used, for example, as a material for a light-emitting layer of an LED.

As the LED including the compound having a perovskite crystal structure of the present invention, for example, a compound having a perovskite crystal structure of the present invention and conductive particles such as ZnS are mixed to form a film, and the single-layer layer is n-type. The transport layer has a p-type transport layer layer structure on one side, and a current is passed through. The hole of the p-type semiconductor and the electron of the n-type semiconductor cancel the charge and emit light in the compound having a perovskite crystal structure on the joint surface. the way.

Further, the compound having a perovskite crystal structure of the present invention can be used as an electron transporting material contained in an active layer of a solar cell.

The solar cell is not particularly limited as long as it has a fluorine-doped tin oxide (FTO) substrate, a titanium oxide dense layer, a porous alumina layer, and a perovskite-type crystal structure of the present invention. The active layer of the compound, a hole such as 2,2',7,7'-tetrakis (N,N'-di-p-methoxyphenylamine)-9,9'-spiro-indole (Spiro-OMeTAD) A solar cell with a transport layer and a silver (Ag) electrode.

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

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

The compound having a perovskite crystal structure of the present invention contained in the active layer functions to charge separation and electron transport.

 [Examples]  

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 a dispersion composition containing a compound having a perovskite crystal structure)    [Example 1]  

A solution of 0.32 mmol of methylammonium 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 was prepared.

Then, 20 mL of toluene was stirred with a magnetic stirrer, and 4 mL of the above solution was added to the toluene. After stirring for 1 hour, the precipitate was separated by centrifugation at 10,000 rpm for 10 minutes to obtain a dispersion composition of the supernatant containing a compound having a perovskite crystal structure.

 [Embodiment 2]  

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

 [Example 3]  

A dispersion liquid composition containing a compound having a perovskite crystal structure was obtained in the same manner as in the above Example 1 except that lead (PbBr ₂ ) was 0.36 mmol and sodium bromide (NaBr) was 0.04 mmol.

When the X-ray diffraction pattern was measured by an X-ray diffraction measuring apparatus (XRD, CuK α line, X'pert PRO MPD, manufactured by Spectris), it was obtained from (hkl)=(001) at a position of 2θ=14°. The diffraction peak was confirmed to have a three-dimensional perovskite crystal structure.

 [Example 4]  

Mixed-ammonium bromide _{(CH 3 NH 3 Br) 0.32mmol} , lead bromide (PbBr ₂₎ 0.388mmol, lithium bromide (LiBr ₂₎ 0.012mmol, n-octylamine 40μL, oleic acid and 1mL DMF10mL, making the solution.

Then, 20 mL of toluene was stirred with a magnetic stirrer, and 4 mL of the above solution was added to the toluene. After stirring for 1 hour, the precipitate was separated by centrifugation at 10,000 rpm for 10 minutes to obtain a dispersion composition of the supernatant containing a compound having a perovskite crystal structure.

 [Example 5]  

A dispersion liquid composition containing a compound having a perovskite crystal structure was obtained in the same manner as in the above Example 4, except that lead bromide (PbBr ₂ ) was 0.38 mmol and lithium bromide (LiBr) was 0.02 mmol.

 [Embodiment 6]  

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

 [Comparative Example 1]  

0.32 mmol of methylammonium 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 were mixed to prepare a solution.

Then, 20 mL of toluene was stirred with a magnetic stirrer, and 4 mL of the above solution was added to the toluene. After stirring for 1 hour, the precipitate was separated by centrifugation at 10,000 rpm for 10 minutes to obtain a dispersion composition of the supernatant containing a compound having a perovskite crystal structure.

When the X-ray diffraction pattern was measured by an X-ray diffraction measuring apparatus (XRD, CuK α line, X'pert PRO MPD, manufactured by Spectris), it was obtained from (hkl)=(001) at a position of 2θ=14°. The diffraction peak was confirmed to have a three-dimensional perovskite crystal structure.

 (Measurement of M substitution amount)  

To 10 mL of the dispersion composition containing the compound having a perovskite crystal structure obtained in Examples 1 to 6 and Comparative Example 1, 1 mL of DMF was added to dissolve a compound having a perovskite crystal structure. The number of moles of M (Na or Li) and B (Pb) in the dissolved solution was measured by ICP-MS (ELAN DRCII, manufactured by Perkin Emer), and the compound having a perovskite crystal structure was used. The amount of M (Na or Li) contained is applied to the formula "M/(M+Pb)" and evaluated.

 (Measurement of quantum yield)  

The absolute PL quantum yield measuring apparatus (manufactured by Hamamatsu Photonics Co., Ltd., trade name C9920-02, measurement conditions: excitation light 450 nm, room temperature, atmospheric pressure) was used to measure the inclusion of calcium obtained in Examples 1 to 6 and Comparative Example 1. Quantum yield of a dispersion composition of a compound of a titanium ore type crystal structure.

The concentration of the compound having a perovskite crystal structure was set to 1000 ppm (μg/g) with respect to the total mass of the dispersion composition, and the quantum yield was measured.

A method of measuring the concentration of a compound having a perovskite crystal structure will be described. To 10 mL of the dispersion composition containing the compound having a perovskite crystal structure obtained in Examples 1 to 6 and Comparative Example 1, 1 mL of DMF was added to dissolve a compound having a perovskite crystal structure. The molar amount of M(Zn) and B(Pb) in the obtained solution was measured by ICP-MS (ELAN DRCII, manufactured by Perkin Emer), and the molar ratio was applied to CH ₃ NH ₃ Pb _(1-a). The concentration of the compound having a perovskite crystal structure was determined by the formula of M _a X _{(3 + δ)} (0 < a ≦ 0.7, 0 ≦ δ ≦ 0.7) or CH ₃ NH ₃ PbBr ₃ .

Table 1 below shows the constitution and quantum yield of the dispersion composition of the compounds having the perovskite crystal structure of Examples 1 to 6 and Comparative Example 1. In Table 1, "M/(M+Pb)" represents a molar ratio obtained by dividing the number of moles of M measured by ICP-MS by the total number of moles of M and B (lead ions).

From the above results, it was confirmed that the dispersion compositions using Examples 1 to 6 of the present invention have a good quantum yield as compared with the dispersion composition of Comparative Example 1 which does not use the present invention.

 (Synthesis of a compound having a perovskite crystal structure)    [Embodiment 7]  

A glass substrate of 2.5 cm x 2.5 cm size 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 bisphosphonate solution having a concentration of 0.1 M. Similarly, sodium bromide (NaBr) was dissolved in a solvent of DMF at 70 ° C to prepare a 0.1 M sodium bromide solution.

Then, methylammonium bromide (CH ₃ NH ₃ Br) was dissolved in a solvent of DMF at 70 ° C to prepare a methylammonium bromide solution having a concentration of 0.1 M. The above lead bromide solution and the sodium bromide solution were mixed so that the molar ratio [Na/(Na+Pb)] became 0.03 to prepare a solution.

Then, the solution was further mixed so as to become a molar ratio [methylammonium bromide / (Zn + Pb)] = 1.

The solution was applied to the glass substrate by a spin coater at a number of revolutions of 1000 rpm, and dried at 100 ° C for 10 minutes in the air to obtain a coating film of the compound.

When the X-ray diffraction pattern of the compound of the coating film was measured by an X-ray diffraction measuring apparatus (XRD, CuK α line, X'pert PRO MPD, manufactured by Spectris), it was obtained at a position of 2θ=14°. A diffraction peak of hkl)=(001) was confirmed to have a three-dimensional perovskite crystal structure.

 [Embodiment 8]  

A coating film of the compound was obtained in the same manner as in the above Example 7 except that the molar ratio [Na/(Na+Pb)] was 0.05.

The X-ray diffraction pattern of the compound of the coating film was measured at a position of 2 θ = 14° when measured by an X-ray diffraction measuring apparatus (XRD, CuK α line, X'pert PRO MPD, manufactured by Spectris). A diffraction peak of (hkl)=(001) was confirmed to have a three-dimensional perovskite crystal structure.

 [Embodiment 9]  

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

 [Embodiment 10]  

A coating film of the compound was obtained in the same manner as in the above Example 7 except that the molar ratio [Na/(Na+Pb)] was 0.30.

 [Comparative Example 2]  

A glass substrate of 2.5 cm x 2.5 cm size 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 prepare a 0.1 M concentration lead trichloride solution. The methylammonium bromide (CH ₃ NH ₃ Br) was dissolved in a solvent of DMF at 70 ° C to prepare a methylammonium bromide solution having a concentration of 0.1 M.

Then, the solution was mixed in such a manner that the molar ratio became (methylammonium bromide) / Pb = 1.

The solution was applied to the glass substrate by a spin coater at a number of revolutions of 1000 rpm, and dried at 100 ° C for 10 minutes to obtain a coating film of the compound.

When the X-ray diffraction pattern of the compound of the coating film was measured by an X-ray diffraction measuring apparatus (XRD, CuK α line, X'pert PRO MPD, manufactured by Spectris Co., Ltd.), it was obtained at a position of 2θ=14°. A diffraction peak of hkl)=(001) was confirmed to have a three-dimensional perovskite crystal structure.

 (Measurement of luminescence spectrum)  

The luminescence spectrum of the coating film of the compound having a perovskite crystal structure obtained in each of Examples 7 to 10 and Comparative Example 2 was measured by a spectrophotometer (manufactured by Shimadzu Corporation, trade name RF-1500, measurement conditions; excitation light). The measurement was performed at 430 nm and sensitivity LOW). Further, the transmittance (%) of the coating film at a wavelength of 430 nm was measured using an ultraviolet visible light absorption spectrophotometer (manufactured by JASCO Corporation, trade name: V-670).

Moreover, the comparison of the luminous intensity between the coating films was performed by correcting the maximum luminous intensity near the wavelength of 530 nm by the following formula (S)-1.

[Maximum luminous intensity near wavelength 530 nm / (100-wavelength transmittance at 430 nm)] × 100 (S) -1

In the formula (S)-1, the maximum intensity in the vicinity of the wavelength 530 nm means the luminescence intensity of the peak of the highest intensity confirmed between the wavelengths of 520 and 540 nm.

Table 2 below shows the structures and maximum luminescence intensity of the compounds having the perovskite crystal structure of Examples 7 to 10 and Comparative Example 2. [M/(M+Pb)] in Table 2 represents the molar ratio of the number of moles of M divided by the total number of moles of M and B (lead ions).

From the above results, it was confirmed that the compounds having the perovskite crystal structure of Examples 7 to 10 of the present invention have good properties as compared with the compound having the perovskite crystal structure of Comparative Example 2 of the present invention. light intensity.

 <<Measurement by ICP-MS>>  

To the compound having a perovskite crystal structure on the glass substrate obtained in Example 8, 1 ml of nitric acid was added to dissolve a compound having a perovskite crystal structure. The dissolved solution was a total of 10 ml of ion-exchanged water, and the amount of Pb and M (Na) was measured by ICP-MS (ELAN DRCII, manufactured by Perkin Emer), and a compound having a perovskite crystal structure was obtained. The amount of M(Na) contained in the sample was evaluated by applying the formula "M/(M+B)".

The value of "Na/(Pb+Na)" of Example 8 was 0.050 based on the measurement result of ICP-MS.

 (Synthesis of a compound having a perovskite crystal structure)    [Example 11]  

A glass substrate of 2.5 cm x 2.5 cm size 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 bisphosphonate solution having a concentration of 0.1 M. Similarly, lithium bromide (LiBr) was dissolved in a solvent of DMF at 70 ° C to prepare a lithium bromide solution having a concentration of 0.1 M.

Then, methylammonium bromide (CH ₃ NH ₃ Br) was dissolved in a solvent of DMF at 70 ° C to prepare a methylammonium bromide solution having a concentration of 0.1 M. The lead bromide solution and the lithium bromide solution were mixed so that the molar ratio [Li/(Li+Pb)] was 0.03 to prepare a solution.

Then, the solution was further mixed in a molar ratio [methylammonium bromide / (Li + Pb)] = 1 .

The solution was applied to the glass substrate by a spin coater at a number of revolutions of 1000 rpm, and dried at 100 ° C for 10 minutes in the air to obtain a coating film of the compound.

 [Embodiment 12]  

A coating film of the compound was obtained in the same manner as in the above Example 11 except that the molar ratio [Li/(Li+Pb)] was 0.05.

 [Example 13]  

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

 (Measurement of luminescence spectrum)  

The luminescence 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 by a spectrophotometer (trade name: RF-1500, manufactured by Shimadzu Corporation), measurement conditions: excitation light. The measurement was performed at 430 nm and sensitivity LOW). Further, the transmittance (%) of the coating film at a wavelength of 430 nm was measured using an ultraviolet visible light absorption spectrophotometer (manufactured by JASCO Corporation, trade name: V-670).

The comparison of the luminous intensity between the coating films was carried out by correcting the maximum luminous intensity near the wavelength of 530 nm by the following formula (S)-1.

[Maximum luminous intensity near wavelength 530 nm / (100-wavelength transmittance at 430 nm)] × 100 (S) -1

Table 3 below shows the structures and maximum luminescence intensity of the compounds having the perovskite crystal structure of Examples 11 to 13 and Comparative Example 2. [M/(M+Pb)] in Table 3 represents the molar ratio of the number of moles of M calculated from the amount of raw material fed by the total number of moles of M and B (lead ions).

From the above results, it was confirmed that the compound having a perovskite crystal structure of the present invention using Examples 11 to 13 of the present invention has a compound having a perovskite crystal structure which does not use Comparative Example 2 of the present invention. Good luminescence intensity.

 (Synthesis of a compound having a perovskite crystal structure)    [Embodiment 14]  

A glass substrate of 2.5 cm x 2.5 cm size 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 bisphosphonate solution having a concentration of 0.1 M. Similarly, sodium bromide (NaBr) was dissolved in a solvent of DMF at 70 ° C to prepare a 0.1 M sodium bromide solution.

Then, methylammonium chloride (CH ₃ NH ₃ Cl) was dissolved in a solvent of DMF at 70 ° C to prepare a methylammonium chloride solution having a concentration of 0.1 M. The above lead bromide solution and sodium bromide solution were mixed so that the molar ratio [Na/(Na+Pb)] became 0.1 to prepare a solution.

Then, the solution was further mixed in a molar ratio [methylammonium chloride / (Na + Pb)] = 1).

The solution was applied to the glass substrate by a spin coater at a number of revolutions of 1000 rpm, and dried at 100 ° C for 10 minutes in the air to obtain a coating film of the compound.

 [Example 15]  

A glass substrate of 2.5 cm x 2.5 cm size 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 bisphosphonate solution having a concentration of 0.1 M. Similarly, sodium bromide (NaBr) was dissolved in a solvent of DMF at 70 ° C to prepare a 0.1 M sodium bromide solution. Then, methylammonium iodide (CH ₃ NH ₃ I) was dissolved in a solvent of DMF at 70 ° C to prepare a methylammonium iodide solution having a concentration of 0.1 M. The above lead bromide solution and sodium bromide solution were mixed so that the molar ratio [Na/(Na+Pb)] became 0.1 to prepare a solution. Then, the solution was further mixed in a molar ratio [methylammonium iodide / (Na + Pb)] = 1 .

The solution was applied to the glass substrate by a spin coater at a number of revolutions of 1000 rpm, and dried at 100 ° C for 10 minutes in the air to obtain a coating film of the compound.

 [Example 16]  

A glass substrate of 2.5 cm x 2.5 cm size 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 bisphosphonate solution having a concentration of 0.1 M. Similarly, lithium bromide (LiBr) was dissolved in a solvent of DMF at 70 ° C to prepare a lithium bromide solution having a concentration of 0.1 M. Then, methylammonium chloride (CH ₃ NH ₃ Cl) was dissolved in a solvent of DMF at 70 ° C to prepare a methylammonium chloride solution having a concentration of 0.1 M. The lead solution of the above was mixed with a lithium bromide solution in such a manner that the molar ratio [Li/Li+Pb]=0.1. Then, the solution was further mixed in a molar ratio [methylammonium chloride/Li+Pb]=1.

The solution was applied to the glass substrate by a spin coater at a number of revolutions of 1000 rpm, and dried at 100 ° C for 10 minutes in the air to obtain a coating film of the compound.

 [Example 17]  

A glass substrate of 2.5 cm x 2.5 cm size 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 bisphosphonate solution having a concentration of 0.1 M. Similarly, lithium bromide (LiBr) was dissolved in a solvent of DMF at 70 ° C to prepare a lithium bromide solution having a concentration of 0.1 M. Then, methylammonium iodide (CH ₃ NH ₃ I) was dissolved in a solvent of DMF at 70 ° C to prepare a methylammonium iodide solution having a concentration of 0.1 M. The above lead bromide solution and the lithium bromide solution were mixed so that the molar ratio [Li/(Li+Pb)] became 0.1 to prepare a solution. Then, the solution was further mixed in a molar ratio [methylammonium iodide / (Li + Pb)] = 1 .

The solution was applied to the glass substrate by a spin coater at a number of revolutions of 1000 rpm, and dried at 100 ° C for 10 minutes in the air to obtain a coating film of the compound.

 [Comparative Example 3]  

A glass substrate of 2.5 cm x 2.5 cm size 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 bisphosphonate solution having a concentration of 0.1 M. Then, methylammonium chloride (CH ₃ NH ₃ Cl) was dissolved in a solvent of DMF at 70 ° C to prepare a methylammonium chloride solution having a concentration of 0.1 M.

Then, the solution was further mixed in a molar ratio [methylammonium chloride / Pb] = 1.

The solution was applied to the glass substrate by a spin coater at a number of revolutions of 1000 rpm, and dried at 100 ° C for 10 minutes in the air to obtain a coating film of the compound.

 [Comparative Example 4]  

A glass substrate of 2.5 cm x 2.5 cm size 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 bisphosphonate solution having a concentration of 0.1 M. Then, methylammonium iodide (CH ₃ NH ₃ I) was dissolved in a solvent of DMF at 70 ° C to prepare a methylammonium iodide solution having a concentration of 0.1 M.

Then, the solution was further mixed in a molar ratio [methylammonium iodide / Pb] = 1.

The solution was applied to the glass substrate by a spin coater at a number of revolutions of 1000 rpm, and dried in the air at 100 ° C for 10 minutes to obtain a coating film of the compound.

 (Measurement of luminescence spectrum)  

The luminescence spectrum of the coating film of the compound having a perovskite crystal structure obtained in each of Examples 14 and 16 and Comparative Example 3 was measured by a spectrophotometer (manufactured by JASCO Corporation, trade name: FT-6500, measurement conditions: excitation light). 430 nm, sensitivity High) was measured. Further, the transmittance (%) of the coating film at 430 nm was measured using an ultraviolet visible light absorption spectrophotometer (manufactured by JASCO Corporation, trade name: V-670).

The comparison of the luminous intensity between the coating films was carried out by correcting the maximum luminous intensity near the wavelength of 500 nm by the following formula (S)-2.

[Maximum luminous intensity near wavelength 500 nm / (100-wavelength 430 nm transmittance)] × 100 (S)-2

In the formula (S)-2, the maximum intensity near the wavelength of 500 nm means the luminescence intensity of the peak of the highest intensity confirmed between the wavelengths of 490 to 510 nm.

 (Measurement of luminescence spectrum)  

The luminescence spectrum of the coating film of the compound having a perovskite crystal structure obtained in each of Examples 15 and 17 and Comparative Example 4 was measured by a spectrophotometer (manufactured by JASCO Corporation, trade name: FT-6500, measurement conditions: excitation light). 430 nm, sensitivity High) was measured. Further, the transmittance (%) of the coating film at 430 nm was measured using an ultraviolet visible light absorption spectrophotometer (manufactured by JASCO Corporation, trade name: V-670).

The comparison of the luminous intensity between the coating films was carried out by correcting the maximum luminous intensity near the wavelength of 540 nm by the following formula (S)-3.

[Maximum luminous intensity near wavelength 540 nm / (100-wavelength transmittance at 430 nm)] × 100 (S) -3

In the formula (S)-3, the maximum intensity in the vicinity of the wavelength of 540 nm means the luminescence intensity of the peak of the highest intensity confirmed between the wavelengths of 530 to 550 nm.

Table 4 below shows the structures and maximum luminescence intensity of the compounds having the perovskite crystal structures of Examples 14 to 17 and Comparative Examples 3 to 4. In Table 4, "M/(M+Pb)" represents the molar ratio of the number of moles of M calculated from the amount of raw material fed by the total number of moles of M and B (lead ions).

From the above results, it was confirmed that the compounds having the perovskite crystal structure of Examples 14 to 17 of the present invention have the compounds having the perovskite crystal structure without using the comparative examples 3 to 4 of the present invention. Good luminescence intensity.

 [Embodiment 18]  

10 mL of DMF was added to cesium bromide (CsBr) so that the concentration of ruthenium was 2700 ppm (μg/g). A solution of 0.35 mmol of lead bromide (PbBr ₂ ), 0.02 mmol of sodium bromide (NaBr), 88 μL of n-octylamine, 1 mL of oleic acid, and the above cesium bromide solution were mixed.

Then, 20 mL of toluene was stirred with a magnetic stirrer, and 4 mL of the above solution was added to the toluene. After stirring for 1 hour, the precipitate was separated by centrifugation at 10,000 rpm for 10 minutes to obtain a dispersion composition of the supernatant containing a compound having a perovskite crystal structure.

 [Comparative Example 5]  

10 mL of DMF was added to cesium bromide (CsBr) so that the concentration of ruthenium was 2700 ppm (μg/g). A solution of 0.4 mmol of lead bromide (PbBr ₂ ), 88 μL of n-octylamine, 1 mL of oleic acid, and the above cesium bromide solution were mixed.

Then, 20 mL of toluene was stirred with a magnetic stirrer, and 4 mL of the above solution was added to the toluene. After stirring for 1 hour, the precipitate was separated by centrifugation at 10,000 rpm for 10 minutes to obtain a dispersion composition of the supernatant containing a compound having a perovskite crystal structure.

 (Measurement of M substitution amount)  

To 10 mL of the dispersion composition containing the compound having a perovskite crystal structure obtained in Example 18, 1 mL of DMF was added to dissolve a compound having a perovskite crystal structure. The number of moles of M(Na) and B(Pb) in the dissolved solution is measured by ICP-MS (ELAN DRCII, manufactured by Perkin Emer) to include a compound having a perovskite crystal structure. The amount of M(Na) is evaluated by applying the formula "M/(M+Pb)".

 (Measurement of quantum yield)  

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 device (manufactured by Hamamatsu Photonics Co., Ltd., trade name C9920-02) The excitation light was 450 nm, and the measurement conditions were as follows: room temperature and atmospheric pressure. The concentration of the compound having a perovskite crystal structure was adjusted to 900 ppm (μg/g) with respect to the total mass of the dispersion composition, and the quantum yield was measured.

 (Measurement of perovskite compounds)  

The concentration of the perovskite compound of the composition obtained in Example 18 and Comparative Example 5 was respectively added to the dispersion containing the perovskite compound and the solvent, and the perovskite was added by adding N,N-dimethylformamide. After the type compound was dissolved, it was measured by ICP-MS (ELAN DRCII, manufactured by Perkin Emer) and an ion chromatography analyzer.

Table 5 below shows the structures and quantum yields of the compounds of the perovskite crystal structure of Example 18 and Comparative Example 5. In Table 5, [M/(M+Pb)] represents a molar ratio obtained by dividing the number of moles of M by the total number of moles of M and B (lead ions).

From the above results, it was confirmed that the present invention using the embodiment 18 of the present invention contains a perovskite type as compared with the dispersion composition containing the compound having a perovskite crystal structure of Comparative Example 5 which does not use the present invention. The dispersion composition of the crystalline structured compound has a good quantum yield.

 [Reference Example 1]  

After the dispersion composition of the present invention described in Examples 1 to 6 is mixed with a resin, the liquid is removed, and the resin composition of the present invention can be obtained, sealed in a glass tube or the like, and then placed in a blue color of the light source. Between the light-emitting diode and the light guide plate, a backlight capable of converting blue light of the blue light-emitting diode into green light or red light is manufactured.

 [Reference Example 2]  

After the dispersion composition described in Examples 1 to 6 is mixed with a resin, the liquid is removed and formed into a sheet, and the resin composition of the present invention can be obtained, and the sealed film is sandwiched between the two barrier films and placed on the light guide plate. A blue light-emitting diode placed on an end surface (side surface) of the light guide plate is produced, and the blue light that is irradiated onto the sheet through the light guide plate can be converted into a backlight of green light or red light.

 [Reference Example 3]  

After the dispersion composition of the present invention described in Examples 1 to 6 is mixed with a resin, the solvent is removed, and the resin composition of the present invention can be obtained, and it can be produced by providing the resin composition of the present invention in the vicinity of the light-emitting portion of the blue light-emitting diode. The blue light is converted into a backlight of green light and red light.

 [Reference Example 4]  

After the dispersion composition of the present invention described in Examples 1 to 6 is mixed with a photoresist, the solvent is removed to obtain a wavelength converting material. The obtained wavelength conversion material is disposed between the blue light-emitting diode of the light source and the light guide plate or the rear portion of the OLED of the light source, and a backlight capable of converting the blue light of the light source into green light or red light is manufactured.

 [Reference Example 5]  

The dispersion liquid compositions described in Examples 1 to 6 and conductive particles such as ZnS were mixed and formed into a film, and a single-area layer n-type transport layer was formed on the single-layer layer p-type transport layer to obtain an LED. By passing a current, the hole of the p-type semiconductor and the electron of the n-type semiconductor can cancel the charge and emit light in the compound having a perovskite crystal structure on the joint surface.

 [Reference Example 6]  

On the surface of the fluorine-doped tin oxide (FTO) substrate, a dense layer of titanium oxide is laminated, a porous alumina layer is laminated thereon, and a calcium-titanium layer is deposited thereon using the dispersion compositions described in Examples 1 to 6. The ore layer, from which 2,2',7,7'-tetrakis (N,N'-di-p-methoxyphenylamine)-9,9'-spiro-indole (Spiro-OMeTAD) is laminated. A hole transport layer is formed thereon, and a layer of silver (Ag) is laminated thereon to fabricate a solar cell.

 [Reference Example 7]  

The dispersion liquid composition containing the compound having a perovskite crystal structure of the present invention described in Examples 1 to 6 is mixed with a resin, and then the solvent is removed to form a crystal structure having a perovskite structure of the present invention. When the resin composition of the compound is disposed in the subsequent stage of the blue light-emitting diode, the blue light which is irradiated from the blue light-emitting diode to the resin molded body is converted into green light and red light to emit white light. Laser diode illumination.

 [Industrial availability]  

According to the present invention, a compound having a perovskite crystal structure having high luminous intensity and a composition having a high quantum yield of a compound having a perovskite crystal structure dispersed in a medium can be provided.

Therefore, the compositions and compounds of the present invention can be suitably used in the field of light-related materials.

Claims (11)

 A composition comprising a compound having a perovskite crystal structure, wherein the compound is composed of A, B, X and M, and the molar amount of M is divided by the total molar amount of M and B. The value of [M/(M+B)] is 0.7 or less; A represents a component of each vertex of a hexahedron centered on B, and X represents a component of each vertex of an octahedron centered at B, A a cerium ion, an organic ammonium ion or a cerium ion located at each vertex of a hexahedron centered on B in the aforementioned perovskite crystal structure; B is a lead ion; M is a monovalent metal selected from the group consisting of cerium ions One or more kinds of cations of the group of cations of the element, at least a part of M is substituted for a part of B in the perovskite crystal structure; and X is eight of B in the perovskite crystal structure The component of each vertex of the surface body is one or more anions selected from the group consisting of chloride ions, bromide ions, fluoride ions, iodide ions, and thiocyanate ions.    The composition according to claim 1, wherein the M is a cation of an alkali metal element.    The composition according to claim 1 or 2, wherein the M is a sodium ion or a lithium ion.    The composition according to any one of claims 1 to 3, wherein the 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.    A compound having a perovskite crystal structure, wherein A, B, X and M are constituent components, and the number of moles of M is divided by the total number of M and B molar ratios [M/( The value of M+B)] is 0.7 or less; A represents a component located at each vertex of a hexahedron centered at B, and X represents a component located at each vertex of an octahedron centered at B; A is located at the foregoing a perovskite-type crystal structure in which a hexahedron at the apex of B is a cerium ion, an organic ammonium ion or a cerium ion; B is a lead ion; M is a sodium ion or a lithium ion, and at least a part of M is in the calcium a part of the substitutional B in the titanium-arc 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 ions, bromide ions, and fluorine. One or more anions of the group consisting of a compound ion, an iodide ion, and a thiocyanate ion.    A film comprising the composition of claim 6 or the compound of claim 7 of the patent application.    A laminate structure having a layer comprising the composition described in claim 6 or the compound described in claim 7 of the patent application.    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 and the liquid crystal panel according to claim 10 of the patent application.