TW201819300A - Compound, dispersion composition, and resin composition - Google Patents

Abstract

The present invention relates to 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 by 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 the center of which is B ion in the perovskite-type crystal structure; B ion is a lead ion; M ion is an aluminum ion, a zinc ion, a cobalt ion, a manganese ion, a gallium ion, a magnesium ion or an indium ion; X ion is Cl-, Br-, F-, I- or SCN- locating at each vertex of an octahedron the center of which is B ion in the perovskite-type crystal structure.

Description

 Compound, dispersion composition and resin composition  

The present invention relates to a compound, a dispersion composition, and a resin composition.

The present application claims the priority of Japanese Patent Application No. 2016-126044, filed on June 24, 2016 in Japan, the content of which is incorporated herein.

Conventionally, a compound having an organic-inorganic perovskite-type crystal structure 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, a dispersion composition containing a quantum compound having a high yield, and a quantum product containing the above compound. A high resin composition.

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 [10].

[1] 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 molar ratio of M and B to the molar ratio [M/ The value of (M+B)] is 0.7 or less; (A is a cerium ion, an organic ammonium ion or a cerium (amidiumium) which is a component of each apex of a hexahedron centered on B in the above-described perovskite crystal structure. An ion; B is a lead ion; M is an aluminum ion, a zinc ion, a cobalt ion, a manganese ion, a gallium ion, a magnesium ion or an indium ion, and at least a part of M replaces a part of B in the aforementioned perovskite crystal structure; A component which is located at each vertex of an 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 anions in groups).

[2] The compound according to [1], wherein the M is an aluminum ion, a zinc ion, a cobalt ion, a manganese ion or a magnesium ion.

[3] The compound according to [1] or [2] wherein the aforementioned M is an aluminum ion, a zinc ion or a magnesium ion.

[4] The compound according to any one of [1] to [3] wherein A is an organic ammonium ion.

[5] A dispersion composition which is a dispersion composition in which a compound according to any one of [1] to [4] is dispersed in a solvent.

[6] A resin composition which is a resin composition in which the compound according to any one of [1] to [4] is dispersed in a resin.

[7] A film comprising the film of the compound according to any one of [1] to [4].

[8] A layered structure having a layer containing the compound according to any one of [1] to [4].

[9] A light-emitting device comprising the laminated structure according to [8] and a light source.

[10] A liquid crystal display comprising the light-emitting device according to [9] and a liquid crystal panel.

According to the present invention, a compound having a perovskite crystal structure having a high luminescence intensity, a dispersion composition containing a quantum yield of the above compound, and a resin composition having a high quantum yield of the above compound 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.

 <compound>  

The compound of the present invention is characterized in that A, B, X and M are constituent components, and the number of moles of M divided by the total number of moles of M and B is the molar ratio [M/(M+B)]. A compound having a perovskite crystal structure of 0.7 or less.

In the present invention, A is a component located at each vertex of a hexahedron centering on B in the perovskite crystal structure, and is a cerium ion, an organic ammonium ion or an amidinium ion.

B is lead ion.

M is an aluminum ion, a zinc ion, a cobalt ion, a manganese ion, a gallium ion, a magnesium ion or an indium ion, and at least a part of M is a part of B in the above-described perovskite crystal structure substitution.

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 anions in groups.

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 . A', B' and X' represent 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 crystal 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 from (hk1)=(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 (hk1) = (100). Confirm that the diffraction peak from (hk1)=(100) is confirmed at a position of 2 θ=13 to 16° from the diffraction peak of (hk1)=(001) or at a position of 2θ=20 to 23°. 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 (hk1)=(002) is usually confirmed at a position of 2θ=1 to 10°. It is better to confirm the diffraction peak from (hk1) = (002) at a position of 2 θ = 2 to 8 °.

In the present invention, the compound having a perovskite crystal structure having A, B, X and M as constituent components is not particularly limited, and may be any structure having a three-dimensional structure, a two-dimensional structure, and a pseudo-two-dimensional structure. compound of.

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) .

Here, the aforementioned a represents the aforementioned molar ratio [M/(M+B)].

The 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 divalent or trivalent metal ion, and X is a monovalent anion, δ can be selected to make the compound neutral (charge 0). .

As a result of intensive studies by the present inventors, it has been found that in a compound having a perovskite crystal structure, a metal cation of the B' component is used as a lead ion (component B), and a part of a plurality of lead ions (component B) is an M component. The luminescence intensity is increased by substitution with aluminum ions, zinc ions, cobalt ions, manganese ions, gallium ions, magnesium ions or indium ions.

At least a part of M of the compound having a perovskite crystal structure of the present invention means a component which replaces a part of lead ions represented by B. In the above basic structure, M exists in a position where the component B (lead ion) is present, a position where the component A is present, or a lattice gap existing in a skeleton constituting the basic structure. However, it is preferred that at least a part of M is substituted for a part of B in the above-described perovskite crystal structure.

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 general formula (1), A is a cerium ion, an organic ammonium ion or a cerium ion, and M is an aluminum ion, a zinc ion, a cobalt ion, a manganese ion, a gallium ion, a magnesium ion or an indium ion, and X is selected. One or more anions in groups 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 ions are replaced by other atoms in the three-dimensional network. Part of it 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 of the present invention, A is a cerium ion, an organic ammonium ion or a cerium ion which is a component of each apex of a hexahedron centering on B in the perovskite crystal structure. In the compound having a perovskite crystal structure of the present invention, when A is a phosphonium ion, an organic ammonium ion having 3 or less carbon atoms or a phosphonium ion having 3 or less carbon atoms, the perovskite crystal structure has a general A 3-dimensional structure represented by AB _(1-a) M _a X ₃ .

Among the compounds, the A system is preferably an organic ammonium ion.

Specific examples of the organic ammonium ion of A include a cation represented by the following formula (A1).

In the formula (A1), R ¹ to R ⁴ each independently represent a hydrogen atom, may have an alkyl group having an amine group as a substituent, or may have a cycloalkyl group having 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]  

In the compound having a perovskite crystal structure, the luminescence intensity can be improved by using the metal cation of the component B as lead and partially replacing a plurality of lead ions with other atoms.

In the compounds of the present invention, at least a portion of M replaces a portion of the lead ions of the metal cation.

More specifically, M is aluminum ion, zinc ion, cobalt ion, manganese ion, gallium ion, magnesium ion or indium ion.

In another aspect of the invention, the aforementioned M is a cation of a divalent or trivalent metal element.

From the viewpoint of maintaining a sufficient crystal structure from the crystal structure of a compound having a perovskite crystal structure, M is preferably aluminum ion, zinc ion, cobalt ion, manganese ion or magnesium ion, and aluminum ion, zinc ion or Magnesium ions are better, and zinc ions are particularly preferred.

M may further contain two or more kinds of ions selected from the group consisting of aluminum ions, zinc ions, cobalt ions, manganese ions, gallium ions, magnesium ions, and indium ions.

 [a]  

From the viewpoint of maintaining a sufficient crystal structure from the crystal structure of a compound having a perovskite crystal structure, the number of moles of M to Pb substituted by M is divided by the total number of moles of M and B. a = [M / (Pb + M)] is greater than 0 and below 0.7. a is preferably 0.01 or more and 0.7 or less, more preferably 0.02 or more and 0.5 or less, still more preferably 0.03 or more and 0.3 or less, and most preferably 0.1 or more and 0.3 or less.

In another aspect of the invention, a is preferably 0.08 or more and 0.25 or less, more preferably 0.15 or more and 0.35 or less.

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 are measured by 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}  

In the compound of the present invention, the value of the aforementioned a, that is, the molar ratio [M/(M+B)] can be measured by ICP-MS (ELAN DRCII, manufactured by Perkin Elmer). The compound having a perovskite crystal structure can be measured by dissolving it with nitric acid, N,N-dimethylformamide or the like.

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 calculated simply by synthesizing the compound of the present invention from the value of the ratio of the ratio of the compound a of the present invention to a desired value.

 [X]  

X is one or more anions selected from the group consisting of chloride ions, bromide ions, fluoride ions, iodide ions, and thiocyanate ions. When X contains a chloride ion or a bromide ion, the content of the chloride ion or the bromide ion is preferably 10 to 100 mol%, more preferably 30 to 100 mol%, based on the total number of moles of X. It is preferably 70 to 100 mol%, and particularly preferably 80 to 100 mol%.

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

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].

When two or more kinds of ions are selected as X, a combination of a bromide ion and a chloride ion or a combination of a bromide ion and an iodide ion is preferred.

A compound having a perovskite crystal structure of the present invention, and a specific example of 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) Zn _a Br ₃ (0<a≦0.7), CH ₃ NH ₃ Pb _(1-a) Al _a Br _(3+δ) (0<a≦0.7, 0<δ≦0.7 ), CH ₃ NH ₃ Pb _(1-a) Co _a Br ₃ (0<a≦0.7), CH ₃ NH ₃ Pb _(1-a) Mn _a Br ₃ (0<a≦0.7), CH ₃ NH ₃ Pb _(1-a) Mg _a Br ₃ (0<a≦0.7), CsPb _(1-a) Zn _a Br ₃ (0<a≦0.7), CsPb _(1-a) Al _a Br _(3+δ) (0<a≦0.7, 0<δ≦0.7), CsPb _(1-a) Co _a Br ₃ (0<a≦0.7), CsPb _(1-a) Mn _a Br ₃ (0<a≦0.7), CsPb _(1-a) Mg _a Br ₃ (0<a≦0.7), CH ₃ NH ₃ Pb( _1-a) Zn _a Br _(3-y) I _y (0<a≦0.7, 0<y<3 ), CH ₃ NH ₃ Pb _(1-a) Al _a Br _(3+δ-y) I _y (0<a≦0.7, 0<δ ≦0.7, 0<y<3), CH ₃ NH ₃ Pb _{( 1-a)} Co _a Br _(3-y) I _y (0<a≦0.7, 0<y<3), CH ₃ NH ₃ Pb _(1-a) Mn _a Br _(3-y) I _y (0 <a≦0.7, 0<y<3), CH ₃ NH ₃ Pb _(1-a) Mg _a Br _(3-y) I _y (0<a≦0.7, 0<y<3), CH ₃ NH _{3 Pb (1-a) Zn a} Br (3-y) Cl y (0 <a ≦ 0.7,0 <y <3), CH 3 NH 3 Pb (1-a) Al a Br (3 + δ- _y) Cl _y (0<a≦0.7, 0<δ≦0.7, 0<y<3), CH ₃ NH ₃ Pb _(1-a) Co _a Br _(3-y) Cl _y (0<a≦0.7 , 0<y<3), CH ₃ NH ₃ Pb _(1-a) Mn _a Br _(3-y) Cl _y (0<a≦0.7, 0<y<3), CH ₃ NH ₃ Pb _{(1- a)} Mg _a Br _(3-y) Cl _y (0<a≦0.7, 0<y<3), (H ₂ N=CH-NH ₂ )Zn _a Br ₃ (0<a≦0.7), (H ₂ N=CH-NH ₂ )Mg _a Br ₃ (0<a≦0.7), (H ₂ N=CH-NH ₂ )Pb _(1-a) Zn _a Br _(3-y) I _y (0<a ≦0.7, 0<y<3), (H ₂ N=CH-NH ₂ )Pb _(1-a) Zn _a Br _(3-y) Cl _y (0<a≦0.7, 0<y<3), etc. Be good. However, the above (3 + δ - y) must be 0 or more.

A specific example of a compound having a perovskite crystal structure represented by A ₂ B _(1-a) M _a X _(4+δ) as a compound having a perovskite crystal structure of the present invention, for example _{(C 4 H 9 NH 3)} 2 Pb (1-a) Zn a Br 4 (0 <a ≦ 0.7), (C 4 H 9 NH 3) 2 Pb (1-a) Mg a Br 4 (0 <a ≦0.7), (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Co _a Br ₄ (0<a≦0.7), (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Mn _a Br ₄ (0<a≦0.7), (C ₇ H ₁₅ NH ₃ ) ₂ Pb _(1-a) Zn _a Br ₄ (0<a≦0.7), (C ₇ H ₁₅ NH ₃ ) ₂ Pb _(1-a) Mg _a Br ₄ (0<a≦0.7), (C ₇ H ₁₅ NH ₃ ) ₂ Pb _(1-a) Co _a Br ₄ (0<a≦0.7), (C ₇ H ₁₅ NH ₃ ) ₂ Pb _{( 1-a)} Mn _a Br ₄ (0<a≦0.7), (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Zn _a Br _(4-y) I _y (0<a≦0.7, 0<y<4), (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Mg _a Br _(4-y) I _y (0<a≦0.7, 0<y<4), (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Co _a Br _(4-y) I _y (0<a≦0.7, 0<y<4), (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Mn _a Br _(4-y) I _y (0<a≦0.7, 0<y<4), (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Zn _a Br _(4-y) Cl _y (0< a≦0.7, 0<y<4), (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Mg _a Br _(4-y) Cl _y (0<a≦0.7, 0<δ≦0.7,0 <y<4) _{(C 4 H 9 NH 3)} 2 Pb (1-a) Co a Br (4-y) Cl y (0 <a ≦ 0.7,0 <y <4), (C 4 H 9 NH 3) 2 Pb ( _{1-a) Mn a Br (} 4-y) Cl y (0 <a ≦ 0.7,0 <y <4) , etc. are preferred.

 ≪luminescence spectrum≫  

The compound having a perovskite crystal structure of the present invention is an illuminant that emits fluorescence in a visible light wavelength region, and when X is a bromide ion, it is usually 480 nm or more, preferably 500 nm or more, more preferably 520 nm or more. Preferably, the phosphor is preferably 700 nm or less, more preferably 600 nm or less, and has a peak in a range of 580 nm or less and a more preferable wavelength range.

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

As still another aspect of the present invention, when X in the compound having a perovskite crystal structure is a bromide ion, the peak of the emitted fluorescence is usually 480 to 700 nm, preferably 500 to 600 nm, and 520 to 520. 580nm is better.

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 still 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 550 730 nm is better.

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 still 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 550nm is better.

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 invention, the compound of the invention comprising a bromide ion as the 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 430 nm transmittance)] × 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 100, more preferably from 20 to 90, still more preferably from 30 to 80.

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 430 nm transmittance)] × 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 50 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 430 nm transmittance)] × 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 10 to 50, more preferably 15 to 30.

 <composition>  

The present invention provides a composition comprising the above compound having a perovskite crystal structure and a solvent and/or a resin.

The above composition may have other components than the compound having a perovskite crystal structure of the present invention described above. As other components, for example, a plurality of impurities and a compound having an amorphous structure in which A, B, X, and/or M are constituent components. 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.

As the composition, for example, a solution composition in which a compound having a perovskite crystal structure of the present invention is dispersed in a solvent, and a dispersion composition in which the compound having a perovskite crystal structure of the present invention is dispersed in a solvent And a resin composition in which the compound having a perovskite crystal structure of the present invention is dispersed in a resin.

 <dispersion composition>  

The dispersion composition of the present invention comprises the above-described compound having a perovskite crystal structure and a liquid, and is a dispersion liquid composition in which a compound having a perovskite crystal structure of the present invention is dispersed in a liquid. By using the compound having a perovskite crystal structure of the present invention as a dispersion composition, the quantum yield can be further improved.

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

In the present specification, the term "dispersed in a liquid" means a state in which particles float or are suspended in a liquid.

The dispersion composition may include a compound having a perovskite crystal structure of the present invention and other components than the liquid. As other components, for example, impurities, A, B, X, and/or M are constituent compounds having a non-crystalline structure and a terminal ligand.

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 components are 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 solvent capable of dispersing the compound having a perovskite crystal structure of the present invention.

The liquid contained in the dispersion composition (excluding the resin) is preferably one which does not easily dissolve the compound having a perovskite crystal structure of the present invention.

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, dimethoxymethane, dimethoxyethane, 1,4-dioxane, 1,3-dioxolane, 4-methyldioxol An ether such as a ring, tetrahydrofuran, methyltetrahydrofuran, anisole or phenethyl ether; methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, butanol, 1- Pentanol, 2-methyl-2-butanol, methoxypropanol, diacetone alcohol, cyclohexanol, 2-fluoroethanol, 2,2,2-trifluoroethanol, 2,2,3,3- Alcohols such as tetrafluoro-1-propanol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, triethylene glycol dimethyl ether, etc. a glycol ether; an organic solvent having a guanamine group such as N,N-dimethylformamide, acetamide, NN-dimethylacetamide; An organic solvent having a nitrile group such as nitrile, isobutyronitrile, propionitrile or methoxyacetonitrile; an organic solvent having a hydrocarbon group such as ethyl carbonate or propyl carbonate; methyl chloride, dichloromethane, chloroform, etc. An organic solvent having a halogenated hydrocarbon group; an organic solvent having a hydrocarbon group such as n-pentane, cyclohexane, n-hexane, benzene, toluene or xylene; dimethyl hydrazine, 1-octadecene.

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 An ether of methoxyethane, 1,4-dioxane, 1,3-dioxolane, 4-methyldioxolane, tetrahydrofuran, methyltetrahydrofuran, anisole, phenylethyl ether, etc.; acetonitrile An organic solvent having a nitrile group such as isobutyronitrile, propionitrile or methoxyacetonitrile; an organic solvent having a carbonate group such as ethyl carbonate or propyl carbonate; methyl chloride, dichloromethane, chloroform An organic solvent having a halogenated hydrocarbon group; an organic solvent having a hydrocarbon group such as n-pentane, cyclohexane, n-hexane, benzene, toluene or xylene, which is considered to have low polarity and is not easily soluble in the present invention. a compound of a mineral crystal structure, which is preferably an organic solvent having a halogenated hydrocarbon group such as methyl chloride, dichloromethane or chloroform; - pentane, cyclohexane, n - hexane, benzene, toluene, xylene, more preferably hydrocarbon-based organic solvent.

The dispersion composition of the present invention may comprise a capping ligand. The term "blocking ligand" refers to a surface which is adsorbed on a particle (a compound having a perovskite crystal structure of the present invention), and a compound which is stably dispersed in a dispersion solvent is used as a terminal ligand, for example, as described later. An ammonium salt represented by the formula (A3) 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) can be adsorbed on the surface of the compound having a perovskite crystal structure of the present invention, or can 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 the following formula (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 the formula (A4) can be adsorbed on the surface of the compound having a perovskite crystal structure of the present invention, or can be dispersed in a solvent.

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

The content of the compound having a perovskite crystal structure of the present invention contained in the dispersion composition is not particularly limited, and the viewpoint of preventing concentration of the compound having a perovskite crystal structure and preventing concentration quenching is not particularly limited. 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 preferably, it is 10 mass ppm or more.

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 of the present invention dispersed in the dispersion composition is not particularly limited, and from the viewpoint of maintaining a sufficient crystal structure, the average particle diameter is preferably 1 nm or more, and 2 nm. More preferably, it is more preferably 3 nm or more, and from the viewpoint that the compound having a perovskite crystal structure of the present invention is less likely to settle, the average particle diameter is preferably 10 μm or less, more preferably 1 μm or less, and 500 nm or less. Better yet.

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 transmission electron microscope (hereinafter also referred to as TEM) or a scanning electron microscope (hereinafter). Also known as SEM) 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 of the present invention contained in the dispersion composition is not particularly limited, and from the viewpoint of maintaining a sufficient 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 of the present invention is less likely to settle, it is preferably 5 μm or less, more preferably 500 nm or less, and 100 nm or less. Better yet.

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 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.

 ≪a's calculation≫  

In the dispersion composition of the present invention, the number of moles of the above M is divided by the value of the molar ratio [M/(M+B)] of the total number of moles of M and B, and ICP-MS (ELAN DRCII, As determined 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 of the present invention.

 Determination of ≪ quantum yield≫  

The quantum yield of the dispersion liquid composition containing the compound having a perovskite crystal structure of the present invention can be an absolute PL quantum yield measuring device (manufactured by Hamamatsu Photonics Co., Ltd., trade name C9920-02, measurement conditions: excitation light) The measurement was carried out at 450 nm, room temperature, and atmosphere. 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%.

Other aspects of the invention include a composition of a compound of the invention comprising cerium ions as component A, wherein the quantum yield measured by the above method is 31% or more.

As the aforementioned quantum yield, it is preferably from 31 to 100%, more preferably from 33 to 80%.

 <Resin composition>  

The resin composition of the present invention comprises the above-described compound having a perovskite crystal structure and a resin of the present invention, which is a resin composition in which a compound having a perovskite crystal structure of the present invention is dispersed in a resin.

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

In the present specification, the term "dispersed in a resin" means a state in which particles are floated or suspended in a resin.

The resin composition may contain a compound having a perovskite crystal structure of the present invention and other components than the resin. The other components are the same as the other components contained in the composition containing the dispersion 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 dispersed in the present invention is not particularly limited, but is a perovskite crystal structure in the temperature at which the resin composition is produced. The solubility of the compound is preferably low.

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

The amount of the compound having a perovskite crystal structure of the present invention 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 total mass of the resin 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 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.

The average particle diameter of the compound having a perovskite crystal structure of the present invention dispersed in the resin composition is not particularly limited, and the compound having a perovskite crystal structure of the present invention dispersed in the dispersion composition is not particularly limited. The average particle size is the same.

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

 ≪a's calculation≫  

In the compound having a perovskite crystal structure of the present invention contained in the resin composition of the present invention, the number of moles of the above M is divided by the molar ratio of M and B to the molar ratio [M/(M+ The value of B)] is the same as the dispersion composition of the present invention described above, and can be measured by ICP-MS (ELAN DRCII, manufactured by Perkin Elmer).

 Determination 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>  

The compound having a perovskite crystal structure of the present invention can be synthesized by a self-assembly reaction using a solution.

For example, a solution containing a lead ion and the above X component, a compound containing the above M component and the X component, and a compound containing the component A and the X component dissolved in a solvent are applied to a substrate, and the solvent can be removed. A compound having a perovskite crystal structure of the present invention.

In another method, a solution containing a lead ion and the X component and a compound containing the M component and the X component dissolved in a solvent are applied to a substrate, and a solvent is removed to form a coating film, and the component A is contained. The solution in which the compound of the above X component is dissolved in a solvent is applied onto the coating film, and the compound having the 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.

As a method of removing a solvent, any one of pressure reduction, drying, and air blowing is performed, and the solvent is volatilized. 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 liquid composition of the present invention includes, for example, a compound containing a lead ion and an X component, a compound containing an M component and an X component, and a compound containing the component A or a compound containing the component A and the component X. a step of dissolving in a solvent to obtain a solution, and a method 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 for producing a substance).

Further, for example, a compound containing a lead ion and an X component, a compound containing the M component and the X component, and a compound containing the component A or a compound containing the component A and the component X are added to a solvent having a high temperature and dissolved. The step of the solution and the method of producing the step of cooling the obtained solution (the second embodiment of the method for producing the dispersion composition).

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

Hereinafter, the following production method will be described. The production method includes dissolving a compound containing a lead ion and an X component, a compound containing the M component and the X component, and a compound containing the component A or a compound containing the component A and the X component. The step of obtaining a solution in a solvent, and the 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 mixing step, and a terminal ligand is added to the solution in which the component A, the component B, the component X and the component M are dissolved, and is added to the crystal structure having a perovskite type. The solubility of the compound is added to a solvent lower than the solvent used in the step of obtaining the solution, or may be a solution in which the components A, B, X, and M are dissolved and the solubility of the compound having a perovskite crystal structure. It is added to both the solvent lower than the solvent used in the step of obtaining a solution.

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 solubility lower than that of the solvent used in the step of obtaining a solution of the perovskite crystal structure may be (a) dropping the solution into the pair having a perovskite crystal. a step in which the solubility of the compound is lower than the solvent used in the step of obtaining the solution, or (b) in the solution, the solubility ratio of the compound having a perovskite crystal structure to the solution is obtained. The step of using a solvent having a low solvent in 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 solvent used for the above-mentioned production method is not particularly limited as long as the solubility of the compound having a perovskite crystal structure is different, and is, for example, selected from the group consisting of methanol, ethanol, 1-propanol, and 2-propanol. -butanol, 2-butanol, third butanol, 1-pentanol, 2-methyl-2-butanol, methoxypropanol, diacetone alcohol, cyclohexanol, 2-fluoroethanol, 2, Alcohols such as 2,2-trifluoroethanol, 2,2,3,3-tetrafluoro-1-propanol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene a glycol ether such as alcohol monoethyl ether acetate or triethylene glycol dimethyl ether; or an amine group having N,N-dimethylformamide, acetamide, NN-dimethylacetamide or the like Organic solvent; esters of dimethyl hydrazine, methyl formate, ethyl formate, propyl formate, amyl formate, methyl acetate, ethyl acetate, amyl acetate; γ-butyrolactone, N-A Ketones such as benzyl-2-pyrrolidone, acetone, dimethyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methylcyclohexanone; diethyl ether, methyl tertiary butyl ether, Diisopropyl ether, dimethoxymethane, dimethoxyethane, 1,4-dioxane, 1,3-dioxane An ether having a nitrile group such as a ring, a 4-methyldioxolane, tetrahydrofuran, methyltetrahydrofuran, anisole or phenethyl ether; or an acetonitrile-based organic solvent such as acetonitrile, isobutyronitrile, propionitrile or methoxyacetonitrile; 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; n-pentane, cyclohexane, and n-hexyl Two kinds of solvents in which a hydrocarbon group-containing organic solvent such as an alkane, benzene, toluene or xylene is grouped.

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 Ethers of methane, dimethoxyethane, 1,4-dioxane, 1,3-dioxolane, 4-methyldioxolan, tetrahydrofuran, methyltetrahydrofuran, anisole, phenylethyl ether, etc. An organic solvent having a nitrile group such as acetonitrile, isobutyronitrile, propionitrile or methoxyacetonitrile; an organic solvent having a carbonate group such as ethyl carbonate or propyl carbonate; methyl chloride, dichloromethane, An organic solvent having a halogenated hydrocarbon group such as chloroform; a hydrocarbon group having n-pentane, cyclohexane, n-hexane, benzene, toluene, xylene, or the like Organic solvents.

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-dimethylacetamidine. An organic solvent having a guanamine group such as an amine 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 an alkane, n-hexane, benzene, toluene or xylene is preferred.

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

The description includes a compound containing a lead ion and an X component, a compound containing the M component and the X component, and a compound containing the component A or a compound containing the component A and the component X, and adding the solvent to a high temperature solvent to dissolve the solution. And a manufacturing method of the step of cooling the obtained solution.

In the above production method, the compound having a perovskite crystal structure of the present invention is precipitated by a difference in solubility due to a temperature difference, whereby a dispersion containing the compound having a perovskite crystal structure of the present invention can be produced.

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.

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 any solvent that dissolves a compound containing a lead ion and an X component, a compound containing the M component and the X component, and a compound containing the component A or a compound containing the component A and the component X. For example, a solvent of 60 to 600 ° C is preferred, and a solvent of 80 to 400 ° C is more preferred.

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

The cooling rate is not particularly limited, and is preferably 0.1 to 1500 ° C / min, more preferably 10 to 150 ° C / min.

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

As a method of taking out a compound having a perovskite crystal structure from a dispersion containing a compound having a perovskite crystal structure, for example, a method of recovering only a compound having a perovskite crystal structure 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 a resin composition of the present invention includes, for example, a step of mixing a compound having a perovskite crystal structure of the present invention or a dispersion composition of the present invention with a solution in which a resin is dissolved in a solvent; The step of removing the solvent.

Further, for example, the following production method includes the steps of: mixing a compound having a perovskite crystal structure of the present invention or a dispersion composition of the present invention with a monomer; and polymerizing the monomer to obtain a resin composition The steps of the object.

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

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

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

In the mixing step of the compound having a perovskite crystal structure or the dispersion liquid 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, the range of 0 to 100 ° C is Good, better in the range of 10 to 80 °C.

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 compound having a perovskite crystal structure of the present invention described above 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-dioxane, 1,3-dioxolane, 4-methyldioxolane, tetrahydrofuran, methyltetrahydrofuran, anisole, phenylethyl ether, etc.; acetonitrile, isobutyronitrile, An organic solvent having a nitrile group such as propionitrile or methoxyacetonitrile; a carbonate-based organic solvent such as ethyl carbonate or propylene carbonate; or a halogenated hydrocarbon group such as methyl chloride, dichloromethane or chloroform. Organic solvent; an organic solvent having a hydrocarbon group such as n-pentane, cyclohexane, n-hexane, benzene, toluene or xylene, which is considered to have low polarity and is not easily soluble in the perovskite crystal structure of the present invention. a compound, which is preferably an organic solvent having a halogenated hydrocarbon group such as methyl chloride, dichloromethane or chloroform; n-pentane or cyclohexane , N - hexane, benzene, toluene, xylene, more preferably an organic solvent having a hydrocarbon group.

The following production method will be described, which includes the step of mixing a compound having a perovskite crystal structure of the present invention or the dispersion composition of the present invention with a monomer; and polymerizing the monomer to obtain a resin composition. 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) constituting the compound having a perovskite crystal structure of the present invention or the dispersion of the present invention. The step of dropping the monomer into the monomer may be the step of (b) dropping the monomer into the compound having the perovskite crystal structure of the present invention or the dispersion composition of the present invention, from the viewpoint of improving dispersibility, (a) is better.

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

In the step of mixing the compound having a perovskite crystal structure 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 in the range of 0 to 100 °C. Preferably, it is preferably in the range of 10 to 80 °C.

The monomer used in the above production method is, 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 of the present invention or a mixture of the dispersion composition of the present invention and a monomer, and a radical polymerization is used. The reaction generates a radical and undergoes a polymerization reaction.

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.

In addition, the technical scope of the present invention is not limited to the above-described embodiments, and various modifications can be added without departing from the spirit and scope of the invention.

 <film>  

The film of the present invention is a film comprising the above-described compound having a perovskite crystal structure of the present invention. The film may be a film comprising the above-described resin composition 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 of the present invention, 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 liquid composition containing a compound having a perovskite crystal structure of the present invention, and a crystal structure having a perovskite type comprising the present invention are used. A method of coating a solution composition of a compound.

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

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

As another aspect of the coating method using the dispersion composition or the solution composition, for example, a dispersion composition further containing a monomer or a solution composition further containing a monomer is coated on a substrate, by removing The solvent polymerizes the monomer to produce the film of the present invention.

 <Laminated structure>  

The laminated structure of the present invention has a laminated structure including a layer of the compound having a perovskite crystal structure of the present invention.

The thickness of the layer containing the compound having a perovskite crystal structure 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 laminated structure of the present invention may have only one layer of a layer containing a compound having a perovskite crystal structure of the present invention, or may have two or more layers.

A layer other than the layer of the present invention having the perovskite crystal structure of the present invention, such as a substrate, a barrier layer, a light scattering layer, or the like, which may be included in the laminated structure of the present invention.

 (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 a compound having a perovskite crystal structure of the present invention from 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 a compound having a perovskite crystal structure of the present invention. Then, 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 method for producing the layer containing the compound having a perovskite crystal structure of the present invention is the same as the method for producing the film of the present invention described above. 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 compound having a perovskite crystal structure, and includes layer light emission of a compound having a perovskite crystal structure, and contains a perovskite type. A device for extracting emitted light from a layer of a compound of crystalline structure. In the light-emitting device of the present invention, a layer containing 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 emitting a layer of 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 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. Using a blue light-emitting diode as a light source, since a layer containing a compound having a perovskite crystal structure is used as a function of a wavelength-converting light-emitting layer, illumination of white light can be realized.

 <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>  

The use of the compound having a perovskite crystal structure of the present invention and a dispersion composition and a resin composition thereof include, for example, an EL display and a wavelength conversion material for a liquid crystal display.

Specifically, for example, (1) the compound having a perovskite crystal structure of the present invention is placed in a glass tube and then sealed, and the blue light-emitting diode of the light source is disposed along the end surface (side surface) of the light guide plate. a backlight that converts blue light into green light or red light (edge type backlight) between the light guide plate, and (2) a compound having a perovskite crystal structure of the present invention is dispersed in a resin or the like to be thinned. The film sealed by the two barrier films is disposed on the light guide plate, and the blue light emitted from the end face (side surface) of the light guide plate passes through the light guide plate, and the blue light irradiated to the sheet is converted into green light and red light. (3) The compound having a perovskite crystal structure of the present invention is dispersed in a resin or the like, and is provided in the vicinity of the light-emitting portion of the blue light-emitting diode, and the irradiated blue light A backlight that is converted into green light or red light (a wafer-type backlight); and (4) a compound having a perovskite crystal structure of the present invention is dispersed in a photoresist. 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 compound having a perovskite crystal structure of the present invention and a dispersion composition and a resin composition thereof, for example, a wavelength conversion material for a laser diode.

Specifically, for example, the compound having a perovskite crystal structure of the present invention is dispersed in a resin or the like to be molded, and is disposed in the subsequent stage of the blue light-emitting diode of the light source to convert blue light into green light and red light. Lighting that emits white light.

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 compound having a perovskite crystal structure)    [Example 1]  

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, zinc bromide (ZnBr ₂ ) was dissolved in a solvent of DMF at 70 ° C to prepare a zinc 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 zinc bromide solution were mixed so that the molar ratio [Zn/(Zn+Pb)] was 0.03 to prepare a solution. Then, the solution was further mixed so that the molar ratio [methylammonium bromide / (Zn + Pb)] became 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.

The X-ray diffraction pattern of the compound of the coating film was measured at an angle 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 (hk1)=(001) was confirmed to have a three-dimensional perovskite crystal structure.

 [Embodiment 2]  

A coating film of the compound was obtained in the same manner as in the above Example 1 except that [Zn/(Zn+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 (hk1)=(001) was confirmed to have a three-dimensional perovskite crystal structure.

 [Example 3]  

A coating film of the compound was obtained in the same manner as in the above Example 1 except that [Zn/(Zn+Pb)] was 0.1.

The X-ray diffraction pattern of the compound of the coating film was measured at an angle 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 (hk1)=(001) was confirmed to have a three-dimensional perovskite crystal structure.

 [Example 4]  

A coating film of the compound was obtained in the same manner as in the above Example 1 except that [Zn/(Zn+Pb)] was 0.2.

 [Example 5]  

A coating film of the compound was obtained in the same manner as in the above Example 1 except that [Zn/(Zn+Pb)] was 0.3.

 [Comparative Example 1]  

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 a molar ratio of 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.

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 (hk1)=(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 1 to 5 and Comparative Example 1 was measured by a spectrophotometer (trade name: RF-1500, manufactured by Shimadzu Corporation). 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: V670).

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 1 below shows the structures and maximum luminescence intensity of the compounds having the perovskite crystal structure of Examples 1 to 5 and Comparative Example 1. In Table 1, "M/(M+Pb)" 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 compound having the perovskite crystal structure of Examples 1 to 5 of the present invention was excellent in comparison with the compound having the perovskite crystal structure of Comparative Example 1 of the present invention. Luminous intensity.

 ≫Measurement by ICP-MS≫  

To the compound having a perovskite crystal structure on the glass substrate obtained in Example 2, 1 ml of nitric acid was added to dissolve a compound having a perovskite crystal structure. The dissolved solution was made up to 10 ml in total with ion-exchanged water, and the number of moles of Pb and M was measured by ICP-MS (ELAN DRCII, manufactured by Perkin Emer), and a compound having a perovskite crystal structure was obtained. The number of M moles contained in the sample was evaluated by applying the formula "M/(M+Pb)".

The value of "M/(M+Pb)" of Example 2 was 0.054 based on the measurement result of ICP-MS.

 (Synthesis of a compound having a perovskite crystal structure)    [Embodiment 6]  

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, zinc bromide (ZnBr ₂ ) was dissolved in a solvent of DMF at 70 ° C to prepare a zinc 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 bromide solution and the zinc bromide solution were mixed so that the molar ratio [Zn/(Zn+Pb)] became 0.1 to prepare a solution. Then, the solution was further mixed in 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.

 [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, zinc bromide (ZnBr ₂ ) was dissolved in a solvent of DMF at 70 ° C to prepare a zinc 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 lead bromide solution and the zinc bromide solution were mixed so that the molar ratio [Zn/(Zn+Pb)] became 0.1 to prepare a solution. Then, the solution was further mixed in 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.

 [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 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 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 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 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.

 (Measurement of luminescence spectrum)  

The luminescence spectrum of the coating film of the compound having a perovskite crystal structure obtained in Example 6 and Comparative Example 2 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: V670).

Moreover, the comparison of the luminous intensity between the coating films is performed 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 in the vicinity of a 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 Example 7 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: V670).

Moreover, the comparison of the luminous intensity between the coating films was performed 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 2 below shows the structures and maximum luminescence intensity of the compounds having the perovskite crystal structure of Examples 6 to 7 and Comparative Examples 2 to 3. In Table 2, "M/(M+Pb)" represents the molar ratio of M, divided by the total molar amount of M and B (lead ion).

From the above results, it was confirmed that the compound having the perovskite crystal structure of Example 6 of the present invention has good luminous intensity compared to the compound having the perovskite crystal structure of Comparative Example 2 which does not use the present invention. .

Further, it was confirmed that the compound having the perovskite crystal structure of Example 7 of the present invention has a good luminescence intensity as compared with the compound having the perovskite crystal structure of Comparative Example 3 which does not use the present invention.

 (Synthesis of a compound having a perovskite crystal structure)    [Embodiment 8]  

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. Similarly, aluminum bromide (AlBr ₃ ) was dissolved in a solvent of DMF at 70 ° C to prepare a 0.1 M aluminum 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 aluminum bromide solution were mixed so that the molar ratio [Al/(Al + Pb)] was 0.03 to prepare a solution. Then, the solution was further mixed in a molar ratio [methylammonium bromide / (Al + 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 9]  

A coating film of a compound having a perovskite crystal structure was obtained by the same method as in the above Example 8 except that [Al/(Al+Pb)] was 0.05.

 [Embodiment 10]  

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. Similarly, at 70 deg.] C so that cobalt bromide (CoBr ₃₎ dissolved in a solvent as DMF to prepare bromide 0.1M solution of cobalt concentration.

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 cobalt bromide solution were mixed so that the molar ratio [Co/(Co+Pb)] was 0.1 to prepare a solution. Then, the solution was further mixed in a molar ratio [methylammonium bromide / (Co + 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.

 [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 DMF at 70 ° C to prepare a 0.1 M concentration lead trichloride solution. Similarly, manganese bromide (MnBr ₃ ) was dissolved in a solvent of DMF at 70 ° C to prepare a manganese chloride 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 above-mentioned lead bromide solution and manganese bromide solution were mixed so that the molar ratio [Mn/(Mn+Pb)] was 0.1 to prepare a solution. Then, the solution was further mixed in a molar ratio [methylammonium bromide / (Mn + 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 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. Similarly, magnesium bromide (MgBr ₃ ) was dissolved in a solvent of DMF at 70 ° C to prepare a magnesium dichloride 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 above lead bromide solution and the magnesium bromide solution were mixed so that the molar ratio [Mg/(Mg+Pb)] was 0.03 to prepare a solution. Then, the solution was further mixed in a molar ratio [methylammonium bromide / (Mg + 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 13]  

A coating film of the compound was obtained in the same manner as in the above Example 12 except that [Mg/(Mg+Pb)] was 0.05.

 [Embodiment 14]  

A coating film of the compound was obtained in the same manner as in the above Example 12 except that [Mg/(Mg+Pb)] was 0.1.

 (Measurement of luminescence spectrum)  

The method of comparing the luminous intensity was carried out in the same manner as in the above Examples 1 to 5 and Comparative Example 1.

Table 3 below shows the structures and maximum luminescence intensity of the compounds having the perovskite crystal structure of Examples 8 to 14 and Comparative Example 1. In Table 3, "M/(M+Pb)" 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 8 to 14 of the present invention have good use as compared with the compound having the perovskite crystal structure of Comparative Example 1 of the present invention. light intensity.

 (Synthesis of a dispersion composition containing a perovskite crystal structure)    [Example 15]  

Mixed methylammonium bromide (CH ₃ NH ₃ Br) 0.32 millimolar, lead bromide (PbBr ₂ ) 0.388 millimolar, zinc bromide (ZnBr ₂ ) 0.012 millimolar, n-octylamine 40 μL, oleic acid 1 mL and 10 ml of DMF were used 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.

 [Example 16]  

A compound containing a perovskite crystal structure was obtained in the same manner as in the above Example 15, except that lead bromide (PbBr ₂ ) was 0.38 mmol and zinc bromide (ZnBr ₂ ) was 0.02 mmol. Dispersion composition.

 [Example 17]  

A compound containing a perovskite crystal structure was obtained in the same manner as in the above Example 15, except that lead bromide (PbBr ₂ ) was 0.36 mmol and zinc bromide (ZnBr ₂ ) was 0.04 mmol. Dispersion composition.

 [Comparative Example 4]  

A solution of 0.35 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 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.

 (Measurement of M substitution amount)  

To 10 mL of the dispersion composition containing the compound having a perovskite crystal structure obtained in each of Examples 15 to 17 and Comparative Example 4, 1 mL of DMF was added to dissolve a compound having a perovskite crystal structure. The amount of M(Zn) 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 number of M(Zn) moles was evaluated by applying the formula "M/(M+Pb)".

 (Measurement of quantum yield)  

The quantum yields of the dispersion compositions containing the compounds having a perovskite crystal structure obtained in Examples 15 to 17 and Comparative Example 4 were 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, and atmospheric pressure) were measured.

The concentration of the compound having a perovskite crystal structure is 1000 ppm (μg/g) with respect to the total mass of the dispersion composition, and the quantum yield is measured for the concentration of the compound having a perovskite crystal structure. The measurement method will be described. To 10 mL of the dispersion composition containing the compound having a perovskite crystal structure obtained in each of Examples 15 to 17 and Comparative Example 4, 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 CH ₃ NH ₃ Pb was applied from the molar ratio _{( 1-a)} Formula of Zn _a Br ₃ (0<a≦0.7) or CH ₃ NH ₃ PbBr ₃ , and the concentration of the compound having a perovskite crystal structure was measured.

Table 4 below shows the structures and quantum yields of the dispersion compositions of the compounds having the perovskite crystal structure of Examples 15 to 17 and Comparative Example 4. In Table 4, "M/(M+Pb)" represents the molar ratio of the molar amount of M measured by ICP-MS divided by the total molar amount of M and B (lead ion).

From the above results, it was confirmed that the inclusion of the composition according to the present invention with respect to Examples 15 to 17 has a calcium-titanium composition as compared with the dispersion composition containing the compound having a perovskite crystal structure of Comparative Example 4 to which the present invention is applied. The dispersion composition of the mineral crystal structure of the compound has a good quantum yield.

 (Synthesis of a dispersion composition containing a perovskite crystal structure)    [Embodiment 18]  

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

0.193 g of lead bromide (PbBr ₂ ) and 0.050 g of zinc bromide (ZnBr ₂ ) and 20 mL of a solvent of 1-octadecene were mixed. The mixture was stirred with a magnetic stirrer while flowing nitrogen gas while heating at 120 ° C for 1 hour, and 2 mL of oleic acid and 2 mL of oleylamine were added. After raising the temperature to 160 ° C, 1.6 mL of the above cesium carbonate solution was added. After the addition, the reaction vessel was immersed in ice water and allowed to cool to room temperature.

Then, the dispersion was centrifuged at 10,000 rpm for 5 minutes to separate a precipitate to obtain a precipitated compound having a perovskite crystal structure.

After dispersing a compound having a perovskite crystal structure in 5 mL of toluene, 50 μL of the dispersion liquid was prepared, and the mixture was further dispersed in 5 mL of toluene to obtain a dispersion liquid containing a compound having a perovskite crystal structure and a solvent. The concentration of the compound having a perovskite crystal structure measured by ICP-MS and an ion chromatography analyzer was 200 ppm (μg/g).

 [Comparative Example 5]  

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

20 mL of a solvent of 0.276 g of lead bromide (PbBr ₂ ) and 1-octadecene was mixed. After stirring with a magnetic stirrer, nitrogen gas was flowed while heating at 120 ° C for 1 hour, and then 2 mL of oleic acid and 2 mL of oleylamine were added. After raising the temperature to 160 ° C, 1.6 mL of the above cesium carbonate solution was added. After the addition, the reaction vessel was immersed in ice water and allowed to cool to room temperature.

Then, the dispersion was centrifuged at 10,000 rpm for 5 minutes to separate a precipitate to obtain a precipitated compound having a perovskite crystal structure.

After the compound having a perovskite crystal structure was dispersed in 5 mL of toluene, 50 μL of the dispersion liquid was prepared, and the mixture was further dispersed in 5 mL of toluene to obtain a dispersion liquid containing a compound having a perovskite crystal structure and a solvent. The concentration of the compound having a perovskite crystal structure measured by ICP-MS and an ion chromatography analyzer was 200 ppm (μg/g).

 (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 amount of M(Zn) and B(Pb) in the dissolved solution is measured by ICP-MS (ELAN DRCII, manufactured by Perkin Emer), and is contained in a compound having a perovskite crystal structure. The number of M(Zn) moles was 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) Measurement conditions: excitation light: 450 nm, room temperature, and atmospheric pressure) were measured. The concentration of the compound having a perovskite crystal structure was adjusted to 200 ppm (μg/g) with respect to the total mass of the dispersion composition, and the quantum yield was measured.

 (Measurement of a compound having a perovskite crystal structure)  

The concentrations of the compounds having a perovskite crystal structure of the compositions obtained in Example 18 and Comparative Example 5 were respectively added to a dispersion containing a compound having a perovskite crystal structure and a solvent by adding N, N- Dimethylcarbamide dissolved a compound having a perovskite crystal structure, and then measured using ICP-MS (ELAN DRCII, manufactured by Perkin Emer) and an ion chromatography analyzer.

Table 5 below shows the constitution and quantum yield of the dispersion composition containing the compound having a perovskite crystal structure of Example 18 and Comparative Example 5. In Table 5, "M/(M+Pb)" represents a molar ratio in which the number of moles of M is divided by the total number of moles of M and B (lead ions).

From the above results, it was confirmed that the inclusion of the perovskite-type crystal according to Example 18 of the present invention was used as compared with the dispersion composition containing the compound having a perovskite crystal structure of Comparative Example 5 of the present invention. The dispersion composition of the constructed compound has a good quantum yield.

 [Reference Example 1]  

The dispersion composition containing the compound having a perovskite crystal structure described in Examples 15 to 18 is mixed with a resin, and then the solvent is removed to obtain a resin composition containing the compound having a perovskite crystal structure of the present invention. After being sealed in a glass tube or the like, it is placed between the blue light-emitting diode of the light source and the light guide plate to convert blue light of the blue light-emitting diode into green light or red light. Backlighting.

 [Reference Example 2]  

The dispersion composition containing the compound having a perovskite crystal structure described in Examples 15 to 18 is mixed with a resin, and then the solvent is removed to form a sheet, whereby the resin containing the compound having a perovskite crystal structure of the present invention can be obtained. The composition is placed on the light guide plate by sandwiching the sealed film with two barrier films, and a blue light-emitting diode placed on the end surface (side surface) of the light guide plate is irradiated to the sheet by the light guide plate. Blue light can be converted into a backlight of green light and red light.

 [Reference Example 3]  

The dispersion composition containing the compound having a perovskite crystal structure described in Examples 15 to 18 is mixed with a resin, and then the solvent is removed to obtain a resin composition containing the compound having a perovskite crystal structure of the present invention. A backlight that converts the irradiated blue light into green light or red light is manufactured by being disposed in the vicinity of the light emitting portion of the blue light emitting diode.

 [Reference Example 4]  

The dispersion composition containing the compound having a perovskite crystal structure described in Examples 15 to 18 was mixed with a photoresist, and then the solvent was 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 compound having a perovskite crystal structure described in Examples 1 to 18 is mixed with conductive particles such as ZnS to form a film, and is formed in a single-area n-type transport layer and in another single-layer p-type transport layer. And get the 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 the perovskite crystal structure described in Examples 1 to 17 is laminated thereon. a compound from which 2,2',7,7'-tetrakis(N,N'-di-p-methoxyphenylamine)-9,9'-spiro-indole (Spiro-OMeTAD), etc. are laminated. The hole transport layer is then laminated with a layer of silver (Ag) to make a solar cell.

 [Reference Example 7]  

When the dispersion liquid composition containing the compound having a perovskite crystal structure described in Examples 15 to 18 is mixed with a resin, and the solvent is removed, the compound containing the perovskite crystal structure of the present invention can be obtained. When the resin composition is disposed in the subsequent stage of the blue light-emitting diode, the laser light emitted from the blue light-emitting diode to the resin molded body is converted into green light and red light to emit white light. Polar body lighting.

 [Industrial availability]  

According to the present invention, a compound having a perovskite crystal structure having a high luminescence intensity, a dispersion composition containing the above compound having a high quantum yield, and a resin composition containing the above compound can be provided.

Therefore, the compound having a perovskite crystal structure, the dispersion composition containing the above compound, and the resin composition using the above compound can be suitably used in the field of light-emitting materials.

Claims (10)

 A compound having a perovskite crystal structure, wherein A, B, X and M are constituents, and the number of moles of M is divided by the molar ratio of M and B to the molar ratio [M/(M+ The value of B)] is 0.7 or less; A is a cerium ion, an organic ammonium ion or a cerium ion which is a component of each apex of a hexahedron centered on B in the above-described perovskite crystal structure; B is a lead ion M is aluminum ion, zinc ion, cobalt ion, manganese ion, gallium ion, magnesium ion or indium ion, at least a part of M is substituted for a part of B in the aforementioned perovskite crystal structure; X represents located in the aforementioned perovskite The component of each apex of the octahedron centered on B in the type crystal structure is one or more selected from the group consisting of chloride ions, bromide ions, fluoride ions, iodide ions, and thiocyanate ions. Anion.    The compound of claim 1, wherein the M is an aluminum ion, a zinc ion, a cobalt ion, a manganese ion or a magnesium ion.    The compound of claim 1 or 2, wherein the aforementioned M is an aluminum ion, a zinc ion or a magnesium ion.    The compound according to any one of claims 1 to 3, wherein the aforementioned A is an organic ammonium ion.    A dispersion composition which is a dispersion composition in which a compound according to any one of claims 1 to 4 is dispersed in a solvent.    A resin composition which is a resin composition in which a compound according to any one of claims 1 to 4 is dispersed in a resin.    A film comprising the compound of any one of items 1 to 4 of the patent application.    A layered structure having a layer comprising a compound according to any one of claims 1 to 4.    A light-emitting device comprising the laminated structure according to item 8 of the patent application and a light source.    A liquid crystal display comprising: the light-emitting device and the liquid crystal panel according to claim 9 of the patent application.