TWI761353B - Composition and compound - Google Patents

Abstract

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

Description

Compositions and Compounds

The present invention relates to compositions and compounds.

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

Conventionally, an organic-inorganic perovskite (Perovskite) compound composed of an organic cation, a halide ion, and a divalent metal ion has been known. In recent years, interest in electrical conductivity and light-emitting properties of compounds having a perovskite-type crystal structure having ions of Group 14 elements (Ge, Sn, and Pb) at the positions of metal ions has been increasing.

In particular, when the aforementioned 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). Furthermore, the emission wavelength can be adjusted depending on the type of halide ion (Non-Patent Document 2).

[Prior Art 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, M. I. Bodnarchuk, F. Krieg, R. Caputo, C.H. Hendon, R.X. Yang, A. Walsh, And M.V. Kovalenko, Nano Letter. 15, 3692-3696 (2015)

However, in order to industrially apply the compounds having a perovskite-type crystal structure as described in Non-Patent Document 1 or Non-Patent Document 2 above as light-emitting materials, further improvements in emission intensity and quantum yield are required.

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

In order to solve the above-mentioned problems, the inventors of the present invention have achieved the following invention as a result of intensive research.

That is, embodiments of the present invention include the inventions of the following [1] to [11].

[1] A composition comprising a compound having a perovskite crystal structure, the compound is obtained by dividing A, B, X and M as constituents, and dividing the molar number of M by the total molar number of M and B The value of the molar ratio [M/(M+B)] of the The composition of the vertex, A is the cesium ion, organic ammonium ion or amidinium ion located at each vertex of the hexahedron with B as the center in the aforementioned perovskite crystal structure; B is the lead ion; M is the selected One or more cations in the group consisting of cations of monovalent metal elements other than cesium ions, at least a part of M replaces a part of B in the perovskite crystal structure; X represents the perovskite crystal structure. The component of each vertex of the octahedron centered on B in the structure is one or more anions selected from the group consisting of chloride ion, bromide ion, fluoride ion, iodide ion and thiocyanate ion ).

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

[3] The composition according to [1] or [2], wherein M is a sodium ion or a lithium ion.

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

[5] The composition according to any one of [1] to [4], which contains a liquid as a medium in the aforementioned composition.

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

[7] A compound having a perovskite crystal structure, which is a molar ratio obtained by dividing the molar number of M by the total molar number of M and B with A, B, X and M as constituent components [ The value of M/(M+B)] is 0.7 or less; (A represents the component located at each vertex of the hexahedron centered on B, X represents the component located at each vertex of the octahedron centered on B, A is the cesium ion, organic ammonium ion or amidinium ion located at each vertex of the hexahedron with B as the center in the aforementioned perovskite crystal structure; B is lead ion; M is sodium ion or lithium ion, and M is at least A part replaces a part of B in the aforementioned perovskite crystal structure; X represents a component located at each vertex of the octahedron with B as the center in the aforementioned perovskite crystal structure, which is selected from chloride ions, bromine one or more anions of the group consisting of compound ion, fluoride ion, iodide ion and thiocyanate ion).

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

[9] A layered structure having a layer containing the composition according to [6] or the compound according to [7]

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

[11] A liquid crystal display including the light-emitting device and liquid crystal panel according to [10].

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

1a‧‧‧The first laminated structure

1b‧‧‧Second layered structure

2‧‧‧Light-emitting device

3‧‧‧LCD monitor

Floor 10‧‧‧

20‧‧‧First substrate

21‧‧‧Second board

22‧‧‧Sealing layer

30‧‧‧Light source

40‧‧‧LCD panel

50‧‧‧Diamond Tablets

60‧‧‧Light guide plate

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

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

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

<Composition>

The present invention includes a composition containing a compound having a perovskite crystal structure, which will be described later. The composition of the present invention is preferably a composition in which a compound having a perovskite crystal structure, which will be described later, is dispersed in a medium.

The said composition may have other components other than the compound which has the said perovskite crystal structure. Other components include, for example, several impurities, and compounds having an amorphous structure containing A, B, X and/or M as constituent components. Examples of impurities include halides containing A, B and/or M; oxides and composite oxides of B and/or M; and other compounds containing A, B, X and/or M.

Examples of the composition in which the compound having a perovskite-type crystal structure is dispersed in a medium include the above-mentioned dispersion composition in which the compound having a perovskite-type crystal structure is dispersed in a liquid, and the above-mentioned composition having a perovskite-type crystal structure. A resin composition in which a structured compound is dispersed in a resin.

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

<Compound with perovskite crystal structure>

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

(A represents a component located at each vertex of a hexahedron centered on B, X represents a component located at each vertex of an octahedron centered on B, and A represents a component located at each vertex of the perovskite crystal structure with B as the center Cesium ion, organic ammonium ion or amidinium ion at each vertex of the central hexahedron; B is lead ion; M is one or more selected from the group consisting of cations of monovalent metal elements other than cesium ions At least a part of M replaces a part of B in the aforementioned perovskite crystal structure.

X represents a component located at each vertex of the octahedron centered on B in the aforementioned perovskite crystal structure, and is selected from the group consisting of chloride ion, bromide ion, fluoride ion, iodide ion and thiocyanate ion One or more anions constituting the group. )

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

In the three-dimensional structure, the perovskite crystal structure is represented by AB _{(1-a) Ma} X _(3+δ) .

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

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

δ is a number that can be appropriately changed according to the charge balance of B and M, and is 0 or more and 0.7 or less. For example, when A is a monovalent cation, B is a divalent cation (Pb ion), M is a monovalent metal ion, and X is a monovalent anion, δ can be selected so that the aforementioned compound is neutral (0 charge).

Generally, the basic structure of a compound having a perovskite crystal structure is a 3-dimensional structure or a 2-dimensional structure.

In a three-dimensional structure, its compositional _formula is represented by A'B'X'3. Here, A' represents an organic cation or an inorganic cation, B' represents a metal cation, and X' represents a halide ion or a thiocyanate ion.

In a two-dimensional structure, its compositional formula is represented by A' ₂ B'X' ₄ . Here, A', B' and X' have the same meanings as described above.

In the above three-dimensional structure, with B' as the center, there is a three-dimensional network in which the vertices represented by B'X' ₆ whose vertices are X' share an octahedron.

In the above 2-dimensional structure, with B' as the center, the octahedron represented by B'X' ₆ whose vertex is X' is shared by 4 vertices X' on the same plane, forming a 2-dimensional connected B'X. A structure in which the layer constituted by ' ₆ and the layer constituted by A' are alternately laminated.

B' is a metal cation that can take the octahedral coordination of X'.

A' is located at each vertex of the hexahedron centered on B'.

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

In the case of the compound having a perovskite crystal structure having a 3-dimensional structure, a diffraction peak derived from (hkl)=(001) is generally confirmed at the position of 2θ=12 to 18° in the X-ray diffraction pattern. Or at the position of 2θ=18 to 25°, confirm the diffraction peak from (hkl)=(100). To confirm the diffraction peak from (hkl)=(001) at the position of 2θ=13 to 16° or confirm the diffraction peak from (hkl)=(100) at the position of 2θ=20 to 23° better.

In the case of the compound having the perovskite crystal structure with the aforementioned 2-dimensional structure, the diffraction peak from (hkl)=(002) is usually confirmed at the position of 2θ=1 to 10° in the X-ray diffraction pattern. , to confirm that the diffraction peak from (hkl)=(002) is better at the position of 2θ=2 to 8°.

As a result of intensive research by the present inventors, it was found that in a compound having a perovskite crystal structure, by making the organic cation or inorganic cation of the A' component a cesium ion, an organic ammonium ion, or an amidinium ion (A component), the metal cation of component B' is lead ion (component B), and a plurality of components A and/or a part of component B are selected from the group consisting of cations of monovalent metal elements other than cesium ions. Substitution of the above cations (M component) can improve the luminous intensity and quantum yield.

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

APb ₍₁ - _a) M _a X _(3+δ )(0<a≦0.7, 0≦δ≦0.7)…(1) [In general formula (1), A is cesium ion, organic ammonium ion or amidinium The ion, M is one or more cations selected from the group consisting of cations of monovalent metal elements other than cesium ions. X is at least one anion selected from the group consisting of chloride ion, bromide ion, fluoride ion, iodide ion, and thiocyanate ion. In the general formula (1), a is more than 0 and 0.7 or less, and δ is 0 or more and 0.7 or less. ]

The basic structural form of general perovskites is ABX ₃ , which has a 3-dimensional network with vertices sharing BX ₆ octahedra. The B component in the ABX ₃ structure is a metal cation capable of taking the octahedral coordination of the X anion. The A cation is located at each vertex of the hexahedron with the B atom as the center, 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 research by the present inventors, it was found that in the basic structure of the perovskite crystal structure represented by ABX ₃ , the metal cation of the B component is lead, and a plurality of lead is replaced by other atoms in the aforementioned three-dimensional network. part of the ions to increase the luminous intensity.

In the present invention, the compound having the perovskite-type crystal structure represented by the general formula (1) has lead, M, and X as main components as components A and B. Here, M refers to an atom that substitutes a part of the lead ion of the metal cation. Moreover, M exists in the position where B component (lead ion) exists in the said basic structure, or replaces the position where A component exists, or exists in the lattice gap which comprises the skeleton of the said basic structure. However, it is preferable that at least a part of M is substituted for a part of B in the aforementioned perovskite crystal structure.

Hereinafter, a compound having a perovskite-type crystal structure comprising A, B, X, and M as constituent components of the present invention will be described.

[A]

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

In a compound having a perovskite crystal structure, when A is a cesium ion, an organic ammonium ion having 3 or less carbon atoms, or an amidinium ion having 3 or less carbon atoms, the general perovskite crystal structure system has the AB _{( 1-a)} 3-dimensional structure represented by M _a X ₃ .

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

In the general formula (A1), R ¹ to R ⁴ each independently represent a hydrogen atom, an alkyl group which may have an amino group as a substituent, or a cycloalkyl group which may have an amino group as a substituent. But R ¹ to R ⁴ will not all be hydrogen atoms.

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

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

The cycloalkyl groups 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 3 to 30, preferably 3 to 11, more preferably 3 to 8.

The groups represented by R ¹ to R ⁴ are preferably a hydrogen atom or an alkyl group.

By reducing the number of alkyl and cycloalkyl groups contained in the general formula (A1) and reducing the number of carbon atoms in the alkyl and cycloalkyl groups, a perovskite crystal with a high luminous intensity can be obtained with a three-dimensional structure Constructed compounds.

When the number of carbon atoms in the alkyl group or the cycloalkyl group is 4 or more, a compound having a part or all of a 2-dimensional and/or quasi-2-dimensional (quasi-2D) perovskite crystal structure can be obtained. When the 2-dimensional perovskite crystal structure is infinitely deposited, it is equivalent to the 3-dimensional perovskite crystal structure (references: P.P.Boix et al, J.Phys.Chem.Lett. 2015, 6, 898-907, etc.).

The total number of carbon atoms contained in the alkyl groups represented by R ¹ to R ⁴ is preferably 1 to 4, and the total number of carbon atoms contained in the cycloalkyl groups represented by R ¹ to R ⁴ is preferably 3 4 is better. More preferably, R ¹ is an alkyl group having 1 to 3 carbon atoms, and R ² to R ⁴ are hydrogen atoms.

With _A as _CH3NH3 ⁺ (also known as methylammonium ion), _{C2H5NH3 +} (also known as _{ethylammonium} ^{ion) or C3H7NH3+} ₍ ^also _known as propylammonium ion ₎ ) is preferred, CH ₃ NH ₃ ⁺ or C ₂ H ₅ NH ₃ ⁺ is more preferred, and CH ₃ NH ₃ ⁺ is even more preferred.

The amidinium ion represented by A includes, for example, the amidinium ion represented by the following general formula (A2).

(R ⁵ R ⁶ N=CH-NR ⁷ R ⁸ ) ⁺ …(A2)

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

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

The number of carbon atoms of the alkyl group represented by R ⁵ to R ⁸ is usually 1 to 20, preferably 1 to 4, more preferably 1 to 3.

The cycloalkyl groups 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 3 to 30, preferably 3 to 11, more preferably 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 in the alkyl group and cycloalkyl group, a perovskite crystal structure having a 3-dimensional structure with high luminescence intensity can be obtained compound of.

When the number of carbon atoms in the alkyl group or the cycloalkyl group is 4 or more, a compound having a part or all of a 2-dimensional and/or quasi-2-dimensional (quasi-2D) perovskite crystal structure can be obtained. Furthermore, the total number of carbon atoms contained in the alkyl groups represented by R ⁵ to R ⁸ is preferably 1 to 4, and the total number of carbon atoms contained in the cycloalkyl groups represented by R ⁵ to R ⁸ is preferably 1 to 4. The number system is preferably 3 to 4. More preferably, R ⁵ is an alkyl group having 1 to 3 carbon atoms, and R ⁶ to R ⁸ are hydrogen atoms.

[M]

M is one or more cations selected from the group consisting of cations of monovalent metal elements other than cesium ions.

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

When M is a sodium ion or a lithium ion, the quantum yield of a composition in which a compound having a perovskite crystal structure is dispersed in a medium is improved. Furthermore, the luminous intensity of the compound having the above-mentioned perovskite crystal structure is also improved.

For the compound having the above-mentioned perovskite crystal structure, the molar ratio [M/( A compound having a perovskite crystal structure with a value of M+B)] of 0.7 or less.

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

The preferred aspects and specific examples of the aforementioned compound having a perovskite crystal structure are better than the compound having a perovskite crystal structure included in the composition of the present invention where M is a sodium ion or a lithium ion. The form and the specific example are the same.

[a]

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

From the viewpoint of maintaining the crystal structure of the compound having a perovskite-type crystal structure and obtaining sufficient light emission intensity or quantum yield, a is greater than 0 and 0.7 or less. From the viewpoint of maintaining the crystal structure of the compound having a perovskite crystal structure and obtaining sufficient luminous intensity or quantum yield, the a series is preferably 0.01 or more and 0.7 or less, more preferably 0.02 or more and 0.5 or less, and 0.03 or more. Below 0.4 is even better.

In another aspect of the present invention, the a series is preferably 0.08 or more and 0.2 or less.

[X]

X is at least one anion selected from the group consisting of chloride ion, bromide ion, fluoride ion, iodide ion, and thiocyanate ion. Among them, chloride ions and bromide ions are preferably used.

When X contains chloride ions or bromide ions, the amount of chloride ions or bromide ions is preferably 10 to 100%, more preferably 30 to 100%, and 70 to 70% relative to the total molar number of X. 100% is better, 80 to 100% is even better.

When X contains two or more kinds of halide ions, the content rate of chloride ions or bromide ions is preferably 10 mol % or more, more preferably 30 mol % or more, relative to the total molar number of X, and More than 70 mol % is more preferable, and more preferably 80 mol % or more.

Among them, X preferably contains bromide ions. When X is two or more kinds of halide ions, the content of the halide ions can be appropriately selected according to the emission wavelength.

As another aspect of the present invention, X preferably contains chloride ions and bromide ions, the content of chloride ions is preferably 20 to 40 mol % relative to the total molar number of X, and the content of bromide ions is preferably 20 to 40 mol%. It is preferably 50 to 80 mol %.

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

The compound having a perovskite crystal structure contained in the composition of the present invention is a specific example of a compound having a three-dimensional perovskite crystal structure represented by AB _(1-a) M _a X _(3+δ) . For example: CH ₃ NH ₃ Pb _(1-a) Na _a Br _(3+δ) (0<a≦0.7, -0.7≦δ<0)CH ₃ NH ₃ Pb _(1-a) Li _a Br _{( 3+δ)} (0<a≦0.7, -0.7≦δ<0)CsPb ₍₁ - _a) Na _a Br _(3+δ) (0<a≦0.7, -0.7≦δ<0), CsPb _{(1 -a)} Li _a Br _(3+δ) (0<a≦0.7, -0.7≦δ<0), CH ₃ NH ₃ Pb _(1-a) Na _a Br _(3+δ-y) I _y (0 <a≦0.7, -0.7≦δ<0, 0<y<3), CH ₃ NH ₃ Pb _(1-a) Li _a Br _(3+δ-y) I _y (0<a≦0.7, -0.7 ≦δ<0, 0<y<3), CH ₃ NH ₃ Pb _(1-a) Na _a Br _(3+δ-y) Cl _y (0<a≦0.7, -0.7≦δ<0, 0<y<3), CH ₃ NH ₃ Pb _(1-a) Li _a Br _(3+δ-y) Cl _y (0<a≦0.7, 0≦δ<0.7, 0<y<3), (H ₂ N=CH-NH ₂ )Pb _(1-a) Na _a Br _(3+δ) (0<a≦0.7, -0.7≦δ<0.7), (H ₂ N=CH-NH ₂ )Pb _{(1- a)} Li _a Br _(3+δ) (0<a≦0.7, -0.7≦δ<0.7), (H ₂ N=CH-NH ₂ )Pb _(1-a) Na _a Br _{(3+δ-y )} I _y (0<a≦0.7, -0.7≦δ<0, 0<y<3), (H ₂ N=CH-NH ₂ )Pb _(1-a) Na _a Br _(3+δ-y) Cl _y (0<a≦0.7, -0.7≦δ<0, 0<y<3) is preferred. However, the aforementioned (3+δ-y) must be 0 or more.

The compound having a perovskite crystal structure contained in the composition of the present invention is a compound having a two-dimensional perovskite crystal structure represented by A ₂ B _(1-a) M _a X _(4+δ) Specific examples, for example: (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Li _a Br _(4+δ) (0<a≦0.7, -0.7≦δ<0.7), (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Na _a Br _(4+δ) (0<a≦0.7, -0.7≦δ<0.7), (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Rb _a Br _(4+δ) (0<a≦0.7, -0.7≦δ<0.7), (C ₇ H ₁₅ NH ₃ ) ₂ Pb _(1-a) Na _a Br _(4+δ) (0<a≦0.7, -0.7≦δ<0.7), (C ₇ H ₁₅ NH ₃ ) ₂ Pb _(1-a) Li _a Br _(4+δ) (0<a≦0.7, -0.7≦δ<0.7), (C ₇ H ₁₅ NH ₃ ) ₂ Pb _(1-a) Rb _a Br _(4+δ) (0<a≦0.7, -0.7≦δ<0.7), (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Na _a Br _(4+δ-y) I _y (0<a≦0.7, -0.7≦δ<0.7, 0<y<4), (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Li _a Br _(4+δ-y) I _y (0<a≦0.7, -0.7≦δ<0.7, 0<y<4), (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Rb _a Br _{(4 +δ-y)} I _y (0<a≦0.7, -0.7≦δ<0.7, 0<y<4), (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Na _a Br _{(4+δ -y)} Cl _y (0<a≦0.7-0.7≦δ<0.7, 0<y<4), (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Li _a Br _(4+δ-y) Cl _y (0<a≦0.7, -0.7≦δ<0.7, 0<y<4), (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Rb _a Br _(4+δ-y) Cl _y (0<a≦0.7, -0.7≦δ<0.7, 0<y<4), etc. are preferred. However, the aforementioned (4+δ-y) must be 0 or more.

<<Luminescence spectrum>>

A compound with a perovskite crystal structure, which emits fluorescence in the visible light wavelength region. When X is a bromide ion, the emission is usually at least 480 nm, preferably at least 500 nm, more preferably at least 520 nm, and at most 700 nm More preferably, it is 600 nm or less, and it is a fluorescent one with a peak in the wavelength range of 580 nm or less.

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

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

When X is an iodide ion, the emission is usually above 520 nm, preferably above 530 nm, more preferably above 540 nm, and usually below 800 nm, preferably below 750 nm, preferably below 730 nm with a peak in the wavelength range Fluorescent.

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

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

When X is a chloride ion, the emission is usually above 300 nm, preferably above 310 nm, more preferably above 330 nm, and usually below 600 nm, preferably below 580 nm, preferably below 550 nm, the wavelength range has The peak fluorescer.

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

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

The maximum emission intensity of the compound having a perovskite crystal structure of the present invention is obtained from the maximum intensity in the visible wavelength region measured using a fluorophotometer and the transmittance of excitation light measured using an ultraviolet-visible light absorptiometry.

As the fluorophotometer, for example, a spectrofluorophotometer RF-1500 (manufactured by Shimadzu Corporation) and a spectrofluorophotometer FT-6500 (manufactured by JASCO Corporation) can be used. As an ultraviolet-visible light absorptiophotometer, for example, an ultraviolet-visible light absorptiometer V-670 (manufactured by JASCO Corporation) can be used.

In the present invention, the maximum emission intensity of the compound can be a value corrected by 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 excitation light.

Pmax/(100-Ep)×100…(S)

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

The maximum emission intensity in the vicinity of the aforementioned wavelength of 530 nm can be obtained by the following formula (S)-1.

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

In the formula (S)-1, the maximum emission intensity near the wavelength of 530 nm refers to the emission 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 10 to 70, more preferably 15 to 60.

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

The maximum emission intensity in the vicinity of the aforementioned wavelength of 500 nm can be obtained by the following formula (S)-2.

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

In the formula (S)-2, the maximum emission intensity in the vicinity of the wavelength of 500 nm refers to the emission intensity of the peak of the highest intensity confirmed between the wavelengths of 490 and 510 nm.

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

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

The maximum emission intensity in the vicinity of the aforementioned wavelength of 540 nm can be obtained by the following formula (S)-3.

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

In the formula (S)-3, the maximum emission intensity in the vicinity of the wavelength of 500 nm refers to the emission intensity of the peak of the highest intensity confirmed between the wavelengths of 530 and 550 nm.

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

In the present invention, the value of a is as described in the following {a calculation method}, which can be obtained by measuring the molarities of M and B in the synthesized compound by an inductively coupled plasma mass spectrometer (hereinafter also referred to as ICP-MS). The value calculated from the value of the ear count.

{a calculation method}

The value of the molar ratio [M/(M+B)] obtained by dividing the molar number of M by the total molar number of M and B in a compound having a perovskite crystal structure is a The compound having a perovskite-type crystal structure is dissolved in a solvent such as nitric acid and N,N-dimethylformamide, and then measured.

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

[M/(M+B)]=(Mmol)/(Mmol+Pbmol)…(T)

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

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

<Dispersion liquid composition>

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

In this specification, the term "liquid" refers to a substance in a liquid state at 1 atm and 25°C.

The dispersion liquid composition system may contain the compound having the above-mentioned perovskite crystal structure and other components than the liquid. As the aforementioned components, for example, impurities, A, B, X, and/or M as constituent components have a compound having an amorphous structure, and a capping ligand.

As impurities, for example, halides containing A, B and/or M; oxides and composite oxides of B and/or M; and other compounds containing A, B, X and/or M. The other components are preferably 10% by mass or less with respect to the total mass of the dispersion composition.

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

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

烷、1,3-二氧戊環、4-甲基二氧戊環、四氫呋喃、甲基四氫呋喃、苯甲醚、苯乙醚等的醚類；甲醇、乙醇、1-丙醇、2-丙醇、1-丁醇、2-丁醇、第3丁醇、1-戊醇、2-甲基-2-丁醇、甲氧基丙醇、二丙酮醇、環己醇、2-氟乙醇、2,2,2-三氟乙醇、2,2,3,3-四氟-1-丙醇等的醇類；乙二醇單甲醚、乙二醇單乙醚、乙二醇單丁醚、乙二醇單乙醚乙酸酯、三乙二醇二甲醚等的二醇醚；N,N-二甲基甲醯胺、乙醯胺、N.N-二甲基乙醯胺等的具有醯胺基的有機溶劑；乙腈、異丁腈、丙腈、甲氧基乙腈等的具有腈基的有機溶劑；碳酸伸乙酯、碳酸伸丙酯等的具有烴基的有機溶劑；氯甲烷、二氯甲烷、三氯甲烷等的具有鹵烴基的有機溶劑；正-戊烷、環己烷、正-己烷、苯、甲苯、二甲苯等的具有烴基的有機溶劑；二甲 基亞碸等。 As the liquid (except resin) contained in the dispersion liquid composition, esters such as methyl formate, ethyl formate, propyl formate, amyl formate, methyl acetate, ethyl acetate, amyl acetate, etc.; γ - ketones such as butyrolactone, N-methyl-2-pyrrolidone, acetone, dimethyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methylcyclohexanone; diethyl ether, Methyl 3rd Butyl Ether, Diisopropyl Ether, Dimethoxymethane, Dimethoxyethane, 1,4-Di

Ethers of alkane, 1,3-dioxolane, 4-methyldioxolane, tetrahydrofuran, methyltetrahydrofuran, anisole, phenethyl ether, etc.; methanol, ethanol, 1-propanol, 2-propanol , 1-butanol, 2-butanol, 3rd butanol, 1-pentanol, 2-methyl-2-butanol, methoxypropanol, diacetone alcohol, cyclohexanol, 2-fluoroethanol, Alcohols such as 2,2,2-trifluoroethanol, 2,2,3,3-tetrafluoro-1-propanol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, Glycol ethers of ethylene glycol monoethyl ether acetate, triethylene glycol dimethyl ether, etc.; N,N-dimethylformamide, acetamide, NN-dimethylacetamide, etc. with amide organic solvents with nitrile groups such as acetonitrile, isobutyronitrile, propionitrile, methoxyacetonitrile, etc.; organic solvents with hydrocarbon groups such as ethylidene carbonate and propylidene carbonate; methyl chloride, dichloromethane , organic solvents with halogenated hydrocarbon groups such as chloroform, n-pentane, cyclohexane, n-hexane, benzene, toluene, xylene and other organic solvents with hydrocarbon groups; dimethyl sulfite and the like.

烷、1,3-二氧戊環、4-甲基二氧戊環、四氫呋喃、甲基四氫呋喃、苯甲醚、苯乙醚等的醚類；乙腈、異丁腈、丙腈、甲氧基乙腈等的具有腈基的有機溶劑；碳酸伸乙酯、碳酸伸丙酯等的具有碳酸酯基的有機溶劑；氯甲烷、二氯甲烷、三氯甲烷等的具有鹵烴基的有機溶劑；正-戊烷、環己烷、正-己烷、苯、甲苯、二甲苯等的具有烴基的有機溶劑，被認為是極性低且不易溶解具有鈣鈦礦型結晶構造的化合物，因而為佳，以氯甲烷、二氯甲烷、三氯甲烷等的具有鹵烴基的有機溶劑；正-戊烷、環己烷、正-己烷、苯、甲苯、二甲苯等的烴基系有機溶劑更佳。 Among these organic solvents, esters such as methyl formate, ethyl formate, propyl formate, amyl formate, methyl acetate, ethyl acetate, amyl acetate, etc.; γ-butyrolactone, acetone, dimethyl formate, etc. Ketones such as base ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methyl cyclohexanone, etc.; diethyl ether, methyl 3-butyl ether, diisopropyl ether, dimethoxymethane, diethyl ether Methoxyethane, 1,4-di

Ethers of alkane, 1,3-dioxolane, 4-methyldioxolane, tetrahydrofuran, methyltetrahydrofuran, anisole, phenethyl ether, etc.; acetonitrile, isobutyronitrile, propionitrile, methoxyacetonitrile Organic solvents with nitrile groups such as ethylidene carbonate, propylene carbonate and other organic solvents with carbonate groups; organic solvents with halogenated hydrocarbon groups such as methyl chloride, dichloromethane, chloroform, etc.; n-pentane Organic solvents with hydrocarbon groups, such as alkane, cyclohexane, n-hexane, benzene, toluene, and xylene, are considered to have low polarity and are difficult to dissolve compounds with a perovskite crystal structure, so methyl chloride is preferred. , dichloromethane, trichloromethane and other organic solvents with halogenated hydrocarbon groups; hydrocarbon-based organic solvents such as n-pentane, cyclohexane, n-hexane, benzene, toluene, xylene, etc. are more preferred.

The dispersion liquid composition of the present invention may contain a capping ligand. The term "capped ligand" refers to a compound that is adsorbed on the surface of a particle (a compound having a perovskite crystal structure) and is stably dispersed in a dispersing solvent. ) and the compound having a carboxyl group represented by (A4). The dispersion liquid composition of the present invention may contain either the ammonium salt represented by the general formula (A3) and the compound having a carboxyl group represented by the general formula (A4), or may contain both.

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

In the general 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 an amine group as a substituent cycloalkyl radicals.

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

The number of carbon atoms of the alkyl group represented by R ⁹ to R ¹² is usually 1 to 20, preferably 5 to 20, more preferably 8 to 20.

The unsaturated hydrocarbon groups represented by R ⁹ to R ¹² may be linear or branched, and may have one amino 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 groups 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 3 to 30, preferably 3 to 20, more preferably 3 to 11.

R ⁹ to R ¹² are preferably hydrogen atoms, alkyl groups or unsaturated hydrocarbon groups. The unsaturated hydrocarbon group is preferably an alkenyl group.

The ammonium salt represented by the general formula (A3) can be adsorbed on the surface of the compound having the above-mentioned perovskite crystal structure, and can also be dispersed in a solvent. The opposite anion of the aforementioned ammonium salt is not particularly limited, for example, halide ions of Br ⁻ , Cl ⁻ , I ⁻ , and F ⁻ .

As the ammonium salt represented by the general formula (A3), a salt of n-octylamine and a salt of oleylamine are preferable.

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

R ¹³ -CO ₂ H…(A4)

In general 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, and may have one carboxyl group as a substituent. The number of carbon atoms of the alkyl group represented by R ¹³ is usually 1 to 20, preferably 5 to 20, more preferably 8 to 20.

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

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

The number of carbon atoms of the cycloalkyl group represented by R ¹³ is usually 3 to 30, preferably 3 to 20, more preferably 3 to 11.

R ¹³ is preferably an alkyl group or an unsaturated hydrocarbon group. The unsaturated hydrocarbon group is preferably an alkenyl group.

The compound having a carboxyl group represented by (A4) can be adsorbed on the surface of the compound having the above-mentioned perovskite crystal structure, and can also be dispersed in a solvent.

The compound having a carboxyl group represented by (A4) is preferably oleic acid.

The content of the above-mentioned compound having a perovskite crystal structure contained in the dispersion composition is not particularly limited, but from the viewpoints of making the compound having a perovskite crystal structure less likely to aggregate and preventing concentration quenching. The total mass of the dispersion liquid composition is preferably 50 mass % or less, more preferably 10 mass % or less, and from the viewpoint of obtaining a sufficient quantum yield, it is preferably 1 mass ppm or more, and 10 mass ppm or more. The mass ppm or more is better.

As another aspect of the present invention, the content of the compound having a perovskite-type crystal structure contained in the dispersion composition is 1 mass ppm or more and 50 mass % or less with respect to the total mass of the dispersion liquid composition. Preferably, it is 10 mass ppm or more and 10 mass % or less.

In this specification, with respect to the total mass of the dispersion composition, the content of the aforementioned compound having a perovskite crystal structure is determined, for example, by ICP-MS, inductively coupled plasma emission spectrometry (hereinafter also referred to as ICP- AES), ion chromatography, etc., can be determined by analyzing the elements constituting the aforementioned perovskite-type crystal structure, and can be determined by measuring a part of the elements constituting the aforementioned perovskite-type crystal structure and calculating from the molar ratio. Determination.

The average particle size of the compound having the perovskite crystal structure dispersed in the dispersion composition is not particularly limited, but from the viewpoint of sufficiently maintaining the crystal structure, the average particle size is preferably 1 nm or more, and more preferably 2 nm or more. The average particle size is preferably 10 μm or less, more preferably 1 μm or less, and even more preferably 500 nm or less, from the viewpoint of making the compound having a perovskite crystal structure less likely to settle.

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

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

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

As another aspect of the present invention, in the particle size distribution of the compound having the perovskite crystal structure contained in the dispersion composition, the median particle size D50 is preferably 3 nm to 5 μm, more preferably 4 nm to 500 nm, 5nm to 100nm is even better.

In the present specification, the particle size distribution of the compound having the perovskite crystal structure dispersed in the dispersion composition can be measured by, for example, TEM or SEM. Specifically, the particle diameters of 20 compounds having a perovskite-type crystal structure dispersed in the dispersion composition were observed by TEM or SEM, and the median particle diameter was obtained from these distributions. D50.

<<Calculation of a>>

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

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

<<Determination of quantum yield>>

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

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

The aforementioned quantum yield is preferably 80 to 100%, more preferably 85 to 100%.

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

The quantum yield is preferably 40 to 100%, more preferably 40 to 80%.

<Resin composition>

The resin composition of the present invention is a composition in which the medium in the composition is a resin, and the compound having the perovskite crystal structure is dispersed in the resin. The quantum yield can be improved by making the above-mentioned compound having a perovskite crystal structure into a resin composition.

In this specification, the "resin" refers to an organic polymer compound.

The resin composition may contain other components than the above-mentioned compound having a perovskite crystal structure and resin. The other components are the same as those that can be contained in the aforementioned dispersion liquid composition of the present invention. The other components are preferably 10% by mass or less with respect to the total mass of the dispersion composition.

The form of the resin composition of the present invention is not particularly limited, and can be appropriately determined according to the application. The resin composition in which the compound having a perovskite-type crystal structure is dispersed may be in the form of a film or formed in the form of a plate.

In the resin composition of the present invention, the resin in which the compound having the perovskite crystal structure is dispersed is not particularly limited, but the temperature at which the resin composition is produced is limited to the compound having the perovskite crystal structure. The lower solubility is preferred.

As the aforementioned resin, for example, polystyrene, methacrylic resin, and the like.

The amount of the compound having a perovskite-type crystal structure contained in the resin composition is not particularly limited, but the aforementioned resins are not particularly limited from the viewpoint of making the compound having a perovskite-type crystal structure less likely to aggregate and preventing concentration quenching. The total mass of the composition is preferably 50 mass % or less, more preferably 10 mass % or less, and from the viewpoint of obtaining a sufficient quantum yield, preferably 1 mass ppm or more, and 10 mass ppm or more better.

As another aspect of the present invention, the content of the compound having a perovskite crystal structure contained in the resin composition is preferably 1 mass ppm or more and 50 mass % or less with respect to the total mass of the resin composition. , more preferably 10 mass ppm or more and 10 mass % or less.

In this specification, the content of the compound having a perovskite crystal structure with respect to the total mass of the resin composition can be measured, for example, by ICP-MS.

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

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

<<Calculation of a>>

In the resin composition of the present invention, the molar ratio [M/(M+B)] obtained by dividing the molar number of M by the total molar number of M and B is the same as the above-mentioned dispersion liquid of the present invention. The composition is the same 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 the above-mentioned dispersion liquid composition of the present invention, and an absolute PL quantum yield measuring device (manufactured by Hamamatsu Photonics Co., Ltd., trade name C9920-02, measuring condition: excitation light can be used) 450 nm, room temperature, atmosphere) for measurement.

<Method for producing compound having perovskite crystal structure>

Compounds having a perovskite crystal structure can be synthesized by self-assembly reactions using solutions.

For example, a solution containing a compound containing Pb and the above-mentioned X, a compound containing the above-mentioned M and the above-mentioned X, and a compound containing the above-mentioned A and the above-mentioned X in a solvent is coated on a substrate, and the solvent is removed. Compounds of mineral crystal structure.

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

At the time of synthesis, a and δ may be set to desired values, and the type and amount of the compound to be prepared above may be adjusted.

As a coating method, for example, a gravure coating method, a bar coating method, a printing method, a spray coating method, a spin coating method, a dipping method, a slit coating method, and the like are mentioned.

As a method for removing the solvent, for example, any one or more of pressure reduction, drying, and air blowing are performed to volatilize the solvent. Drying may be performed at normal temperature or may be heated. The temperature during heating can be appropriately determined in consideration of the time required for drying and the heat resistance of the substrate, and is preferably 50 to 200°C, more preferably 50 to 100°C.

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

Among them, N-methyl-2-pyrrolidone, N,N-dimethylformamide, acetamide, N-methyl-2-pyrrolidone, N,N-dimethylformamide, acetamide, Organic solvents having an amide group such as N,N-dimethylacetamide, and dimethylsulfoxide are suitable, and among them, N,N-dimethylformamide is more suitable.

The above-mentioned organic solvent may have a branched structure or a cyclic structure, may have a plurality of functional groups such as -O-, -CO, -COO-, and -OH, and hydrogen atoms may be substituted with halogen atoms 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, with respect to the total mass of the solution.

<Manufacturing method of dispersion liquid composition>

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

For example, as a production method of the dispersion liquid composition of the present invention, for example, a production method comprising the following steps: a compound comprising components B and X, a compound comprising components M and X, a compound comprising A, or a compound comprising A and X The step of dissolving the compound in a solvent to obtain a solution; and the step of mixing the obtained solution with a solvent having a lower solubility for the compound having a perovskite crystal structure than the solvent used in the step of obtaining the solution (dispersion composition 1st implementation aspect).

Further, for example, a production method comprising the steps of adding a compound containing B and X, a compound containing M and X, a compound containing A, or a compound containing A and X to a high-temperature solvent, and dissolving it to obtain a solution and cooling the obtained solution (the second embodiment of the dispersion composition).

<The first embodiment of the dispersion composition>

Hereinafter, the following manufacturing method will be described, which comprises the steps of dissolving a compound containing B and X, a compound containing M and X, a compound containing A, or a compound containing A and X in a solvent to obtain the step of obtaining a solution; and the step of mixing the obtained solution with a solvent having a lower solubility in the compound having a perovskite crystal structure than that used in the step of obtaining the solution.

In addition, the so-called solubility refers to the solubility at the temperature at which the mixing step is performed.

The aforementioned production method preferably includes a step of adding a capping ligand from the viewpoint of stably dispersing a compound having a perovskite crystal structure. The capping ligand is preferably added before the aforementioned mixing step. The capping ligand is added to the solution in which A, B, X and M are dissolved, and the solubility ratio to the compound having a perovskite crystal structure is added. The solvent used in the step of obtaining the solution is added to a low solvent, or it can also be added to the solution in which A, B, X and M are dissolved and the solubility of the compound having a perovskite crystal structure is higher than that used in the step of obtaining the solution. Solvents with low solvent are added to both.

The aforementioned production method preferably includes a step of removing coarse particles by means of centrifugation, filtration, or the like after the aforementioned mixing step. The size of the coarse particles removed by the aforementioned removing step is preferably 10 μm or more, more preferably 1 μm or more, and even more preferably 500 nm or more.

The step of mixing the aforementioned solution with a solvent having a lower solubility to the compound having a perovskite-type crystal structure than the solvent used in the step of obtaining the aforementioned solution may be (a) dropping the aforementioned solution into a compound having a perovskite-type crystal structure. The step in which the solubility of the compound having the crystal structure is lower than that of the solvent used in the step of obtaining the solution may be (b) in the aforementioned solution, and the solution may be obtained by adding dropwise to the compound having the perovskite crystal structure the solubility of which is lower than that of the solvent. (a) is preferable from the viewpoint of improving the dispersibility in the step with a low solvent used in the step.

It is preferable from the viewpoint of improving the dispersibility that stirring is performed at the time of dropping.

In the step of mixing the aforementioned solution with a solvent having a lower solubility to the compound having a perovskite-type crystal structure than the solvent used in the step of obtaining the aforementioned solution, the temperature is not particularly limited, but is only necessary to ensure that the compound has a perovskite-type crystal structure. From the viewpoint of the easiness of precipitation of the compound, the range of 0 to 40°C is preferable, and the range of 10 to 30°C is more preferable.

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

烷、1,3-二氧戊環、4-甲基二氧戊環、四氫呋喃、甲基四氫呋喃、苯甲醚、苯乙醚等的醚類；乙腈、異丁腈、丙腈、甲氧基乙腈等的具有腈基的有機溶劑；碳酸伸乙酯、碳酸伸丙酯等的具有碳酸酯基的有機溶劑；氯甲烷、二氯甲烷、三氯甲烷等的具有鹵烴 基的有機溶劑；正-戊烷、環己烷、正-己烷、苯、甲苯、二甲苯等的具有烴基的有機溶劑所構成群組的2種溶劑。 There are no particular limitations on the two solvents that are used in the above-mentioned production method and have different solubility for the compound having a perovskite crystal structure, and for example, are selected from methanol, ethanol, 1-propanol, 2-propanol, 1- Butanol, 2-butanol, 3rd butanol, 1-pentanol, 2-methyl-2-butanol, methoxypropanol, diacetone alcohol, cyclohexanol, 2-fluoroethanol, 2,2 ,2-trifluoroethanol, 2,2,3,3-tetrafluoro-1-propanol and other alcohols; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol Glycol ethers such as monoethyl ether acetate, triethylene glycol dimethyl ether, etc.; organic amide groups such as N,N-dimethylformamide, acetamide, NN-dimethylacetamide, etc. Solvents; esters of dimethyl sulfoxide, methyl formate, ethyl formate, propyl formate, amyl formate, methyl acetate, ethyl acetate, amyl acetate, etc.; γ-butyrolactone, N-methyl - Ketones such as 2-pyrrolidone, acetone, dimethyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methyl cyclohexanone, etc.; diethyl ether, methyl 3-butyl ether, diethyl ether Isopropyl ether, dimethoxymethane, dimethoxyethane, 1,4-di

Ethers of alkane, 1,3-dioxolane, 4-methyldioxolane, tetrahydrofuran, methyltetrahydrofuran, anisole, phenethyl ether, etc.; acetonitrile, isobutyronitrile, propionitrile, methoxyacetonitrile Organic solvents with nitrile groups such as ethylidene carbonate, propylene carbonate and other organic solvents with carbonate groups; organic solvents with halogenated hydrocarbon groups such as methyl chloride, dichloromethane, chloroform, etc.; n-pentane Two kinds of solvents in the group consisting of organic solvents having hydrocarbon groups such as alkane, cyclohexane, n-hexane, benzene, toluene, and xylene.

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

烷、1,3-二氧戊環、4-甲基二氧戊環、四氫呋喃、甲基四氫呋喃、苯甲醚、苯乙醚等的醚類；乙腈、異丁腈、丙腈、甲氧基乙腈等的具有腈基的有機溶劑；碳酸伸乙酯、碳酸伸丙酯等的具有碳酸酯基的有機溶劑；氯甲烷、二氯甲烷、三氯甲烷等的具 有鹵烴基的有機溶劑；正-戊烷、環己烷、正-己烷、苯、甲苯、二甲苯等的具有烴基的有機溶劑。 The solvent included in the mixing step of the aforementioned production method is preferably a solvent with low solubility for the compound having a perovskite crystal structure. For example, when the aforementioned step is performed 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, etc.; γ-butyrolactone, N-methyl-2-pyrrolidone, acetone , dimethyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methyl cyclohexanone and other ketones; diethyl ether, methyl 3-butyl ether, diisopropyl ether, dimethoxy Methane, Dimethoxyethane, 1,4-Di

Ethers of alkane, 1,3-dioxolane, 4-methyldioxolane, tetrahydrofuran, methyltetrahydrofuran, anisole, phenethyl ether, etc.; acetonitrile, isobutyronitrile, propionitrile, methoxyacetonitrile Organic solvents with nitrile groups such as ethylidene carbonate, propylene carbonate and other organic solvents with carbonate groups; organic solvents with halogenated hydrocarbon groups such as methyl chloride, dichloromethane, chloroform, etc.; n-pentane Organic solvents having hydrocarbon groups such as alkane, cyclohexane, n-hexane, benzene, toluene, and xylene.

Among the two solvents with different solubility, the solubility difference is preferably 100μg/solvent 100g to 90g/solvent 100g, and more preferably 1mg/solvent 100g to 90g/solvent 100g. From the viewpoint of a solubility difference of 100 μg/100 g of solvent to 90 g/100 g of solvent, for example, when the mixing step is performed at room temperature (10° C. to 30° C.), the solvent used in the step of obtaining a solution is N.N-dimethylacetamide and other organic solvents with amide groups or dimethyl sulfoxide, and the solvents used in the mixing step are organic solvents with halogenated hydrocarbon groups such as methyl chloride, dichloromethane, chloroform, etc.; n-pentane, cyclohexane , n-hexane, benzene, toluene, xylene and other organic solvents having hydrocarbon groups are preferred.

<Second Embodiment of the Manufacturing Method of the Dispersion Composition>

Hereinafter, a production method comprising the steps of adding a compound containing B and X, a compound containing M and X, a compound containing A, or a compound containing A and X to a high-temperature solvent and dissolving it will be described. the step of solution; and the step of cooling the obtained solution.

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

From the viewpoint of stably dispersing the perovskite compound, the aforementioned production method preferably includes a step of adding a capping ligand.

The aforementioned production method preferably includes a step of removing coarse particles by a method such as centrifugation or filtration after the cooling step. The size of the coarse particles removed by the aforementioned removing step is preferably 10 m or more, more preferably 1 m or more, and still more preferably 500 nm or more.

Here, the so-called high-temperature solvent may be a solvent at a temperature at which the compound containing B and X, the compound containing A, or the compound containing A and X is dissolved, for example, a solvent of 60 to 600° C. A solvent at 400°C is better.

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

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

The solvent used in the aforementioned production method is not particularly limited as long as it can dissolve the compound containing B and X, the compound containing M and X, the compound containing component A, or the compound containing component A and component X, for example It is the same as the liquid (except resin) contained in the said dispersion liquid composition.

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

The method of the aforementioned solid-liquid separation includes, for example, a method such as filtration, a method using evaporation of a solvent, and the like.

<Manufacturing method of resin composition>

For example, as a method for producing the resin composition of the present invention, there may be mentioned a production method comprising the step of dissolving the above-mentioned compound having a perovskite crystal structure or the dispersion liquid composition of the present invention with a solution in which the resin is dissolved in a solvent. a step of mixing; and a step of removing the solvent.

Furthermore, a production method comprising the steps of mixing the above-mentioned compound having a perovskite crystal structure or the dispersion liquid composition of the present invention with a monomer, and polymerizing the monomer to obtain a resin composition can be exemplified. A step of.

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

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

Stirring during mixing is preferable from the viewpoint of improving dispersibility.

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

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

The solvent for dissolving the resin is not particularly limited as long as it can dissolve the resin, but it is preferably one that does not easily dissolve the perovskite compound.

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

烷、1,3-二氧戊環、4-甲基二氧戊環、四氫呋喃、甲基四氫呋喃、苯甲醚、苯乙醚等的醚類；乙腈、異丁腈、丙腈、甲氧基乙腈等的具有腈基的有機溶劑；碳酸伸乙酯、碳酸伸丙酯等的具有碳酸酯系的有機溶劑；氯甲烷、二氯甲烷、三氯甲烷等的具有鹵烴基的有機溶劑；正-戊烷、環己烷、正-己烷、苯、甲苯、二甲苯等的具有烴基的有機溶劑，被認為是極性低且不易溶解鈣鈦礦化合物，因而為佳，以氯甲烷、二氯甲烷、三氯甲烷等的具有鹵烴基的有機溶劑；正-戊烷、環己烷、正-己烷、苯、甲苯、二甲苯等的具有烴基的有機溶劑更佳。 Among them, esters such as 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, methyl cyclohexanone, etc.; diethyl ether, methyl 3-butyl ether, diisopropyl ether, dimethoxymethane, dimethoxyethane , 1,4-two

Ethers of alkane, 1,3-dioxolane, 4-methyldioxolane, tetrahydrofuran, methyltetrahydrofuran, anisole, phenethyl ether, etc.; acetonitrile, isobutyronitrile, propionitrile, methoxyacetonitrile Organic solvents with nitrile groups such as ethylidene carbonate and propylidene carbonate; organic solvents with carbonate groups such as ethylidene carbonate and propylidene carbonate; organic solvents with halogenated hydrocarbon groups such as methyl chloride, dichloromethane, chloroform, etc.; n-pentane Organic solvents with hydrocarbon groups such as alkane, cyclohexane, n-hexane, benzene, toluene, xylene, etc. are considered to be low in polarity and difficult to dissolve perovskite compounds, so it is preferable to use methyl chloride, dichloromethane, An organic solvent having a halogenated hydrocarbon group such as chloroform, and an organic solvent having a hydrocarbon group such as n-pentane, cyclohexane, n-hexane, benzene, toluene, and xylene are more preferable.

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

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

From the viewpoint of improving dispersibility, those that are stirred during mixing are preferred.

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

Examples of monomers used in the aforementioned production method include styrene and methyl methacrylate.

In the above-mentioned production method, as a method of polymerizing a monomer, a known polymerization reaction such as radical polymerization can be appropriately used. For example, in the case of radical polymerization, a radical polymerization initiator is added to the above-mentioned compound having a perovskite crystal structure or the mixture of the dispersion liquid composition of the present invention and a monomer, and a polymerization reaction by generating radicals is used, Free radicals are generated and the polymerization reaction proceeds.

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

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

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 gist of the present invention.

<film>

The film of the present invention is a film containing the resin composition of the present invention or a film containing the compound having a perovskite crystal structure of the present invention.

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

In this specification, the thickness of the said film can be measured by a micrometer at three arbitrary points, and can be obtained by calculating the average value.

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

<Production method of 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 the solution is the same as that of the above-mentioned production method of the compound of the present invention.

As another method of the manufacturing method of the film of this invention, the coating method using a dispersion liquid composition in this invention is mentioned, for example.

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

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

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

<Layered Structure>

The layered structure of the present invention is a layered structure having a layer comprising the resin composition of the present invention, or a layered structure having a layer comprising the compound having a perovskite crystal structure of the present invention.

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

In this specification, the thickness of the said film can be measured by a micrometer at three arbitrary points, and can be obtained by calculating the average value.

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

Examples of layers other than the layer containing the resin composition of the present invention or the layer containing the compound having a perovskite crystal structure of the present invention that the laminated structure of the present invention may have include a substrate, a barrier layer, a light scattering layer, and the like. .

(substrate)

The substrate is not particularly limited, but from the viewpoint of extracting emitted light, a transparent substrate is preferred. As a board|substrate, the flexible board|substrate and glass substrate which consist of polyethylene terephthalate etc. are mentioned, for example.

(barrier layer)

The term "barrier layer" refers to a layer having a function of protecting the layer containing the resin composition of the present invention or the layer containing the 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, but is preferably a transparent layer from the viewpoint of extracting emitted light. As the barrier layer, for example, a known 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 emitted light.

The light scattering layer is not particularly limited, but is preferably a transparent layer from the viewpoint of extracting emitted light. Examples of the light-scattering layer include a layer containing light-scattering particles such as silicon oxide particles, and an amplifying diffusion film.

FIG. 1 is a schematic cross-sectional view showing the configuration of the laminated structure of the present embodiment. The first layered structure 1a is provided between the first substrate 20 and the second substrate 21, and the layer 10 containing the resin composition of the present invention or the compound having a perovskite crystal structure of the present invention is provided. Furthermore, 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 , a layer 10 including a compound having a perovskite crystal structure of the present invention located between the first substrate 20 and the second substrate 21 , and sealing A layered structure characterized in that the sealing layer is disposed on the surface of the layer 10 containing the compound having the perovskite crystal structure and not in contact with the first substrate 20 and the second substrate 21. 1a.

In another aspect of the present invention, the laminate 50, the light guide plate 60, and the laminated structure 1b of the first laminated structure 1a are laminated in this order.

<Manufacturing method of laminated structure>

The method for producing the layer comprising the resin composition of the present invention and the layer comprising 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 film production method of the present invention and a conventional method.

<Light-emitting device>

The light-emitting device of the present invention is a light-emitting device including the laminated structure of the present invention and a light source. When light emitted from a light source is irradiated on a laminated structure, it is absorbed by a layer containing a resin composition or a compound having a perovskite crystal structure, and the layer containing the resin composition or a compound having a perovskite crystal structure emits light. , a device for extracting emitted light from a layer containing a resin composition or a compound having a perovskite crystal structure. In the light-emitting device of the present invention, a layer containing a resin composition or a compound having a perovskite crystal structure generally functions as a wavelength-converting light-emitting layer.

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

In the light-emitting device of the present invention, the layered structure of the present invention may have layers other than those described above, for example, a light reflection member layer, a brightness enhancement layer, a wafer, a light guide plate, and a dielectric material layer between components.

(light source)

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

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

Another specific example of the light-emitting device of the present invention is, for example, lighting. By using a blue light-emitting diode as a light source, a layer containing a resin composition or a compound having a perovskite-type crystal structure functions as a wavelength-converting light-emitting layer, enabling white light-emitting illumination.

<Liquid crystal display>

As shown in FIG. 2 , the liquid crystal display 3 of the present embodiment includes a liquid crystal panel 40 and the light-emitting device 2 of the present embodiment in this order from the viewing side. The light-emitting device 2 includes the second laminated structure 1 b and the light source 30 . The second build-up structure 1b is the above-described first build-up structure 1a further including the glazing sheet 50 and the light guide plate 60. The display may be further provided with any suitable other components.

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

<Use>

As the application of the compound having a perovskite crystal structure of the present invention and the dispersion liquid composition and resin composition containing the same, for example, wavelength conversion materials for EL displays and liquid crystal displays can be cited, and specifically, (1 ) Put the compound having the perovskite crystal structure of the present invention into a glass tube and seal it, arrange it between the blue light-emitting diode of the light source and the light guide plate along the end face (side surface) of the light guide plate, and place the Backlight that converts blue light into green light and red light (edge-type backlight); (2) The compound having a perovskite crystal structure of the present invention is dispersed in a resin or the like to form flakes, and this is sealed with two barrier films. The film is arranged on the light guide plate, and from the blue light-emitting diode placed on the end face (side) of the light guide plate, through the light guide plate, the blue light irradiated on the sheet is converted into green light and red light. (3) Disperse the compound having a perovskite crystal structure of the present invention in a resin, etc., and arrange it in the vicinity of the light-emitting part of the blue light-emitting diode, and convert the irradiated blue light into green light and red light (4) Disperse the compound having a perovskite crystal structure of the present invention in a photoresist. A backlight that is provided on a color filter and converts blue light irradiated from a light source to green light and red light.

Examples of applications of the composition comprising the compound having a perovskite crystal structure of the present invention include wavelength conversion materials for laser diodes. Specifically, the composition including the compound having a perovskite-type crystal structure of the present invention is molded, arranged in the rear stage of the blue light-emitting diode of the light source, and converts blue light into green light and red light and emits it. Illumination with white light.

Furthermore, 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 an LED containing the compound having a perovskite crystal structure of the present invention, for example, the compound having a perovskite crystal structure of the present invention and conductive particles such as ZnS are mixed and laminated in a film form, and an n-type single-area layer is formed. The transport layer has a structure in which a p-type transport layer is laminated on the other side. When a current flows, the holes of the p-type semiconductor and the electrons of the n-type semiconductor cancel the charges in the compound having the perovskite crystal structure at the junction surface and emit light. Way.

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

As the aforementioned solar cell, its structure is not particularly limited, for example, a fluorine-doped tin oxide (FTO) substrate, a titanium oxide dense layer, a porous aluminum oxide layer, a perovskite crystal structure comprising the present invention in this order are included. The active layer of the compound, the holes of 2,2',7,7'-tetrakis(N,N'-di-p-methoxyphenylamine)-9,9'-spiro-OMeTAD, etc. Solar cells with transport layers and silver (Ag) electrodes.

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

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

The compound having a perovskite crystal structure of the present invention contained in the active layer functions to separate charges and transport electrons.

[Example]

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

(Synthesis of dispersion liquid composition containing compound having perovskite crystal structure) [Example 1]

Methylammonium bromide (CH ₃ NH ₃ Br) 0.32 mmol, lead bromide (PbBr ₂ ) 0.388 mmol, sodium bromide (NaBr) 0.012 mmol, n-octylamine 40 μL, oleic acid 1 mL, and DMF 10 mL were mixed to prepare a solution.

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

[Example 2]

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

[Example 3]

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

When the X-ray diffraction pattern is measured with an X-ray diffraction measuring apparatus (XRD, CuK α line, X'pert PRO MPD, manufactured by Spectris), the X-ray diffraction pattern has a value from (hkl)=(001) at the position of 2θ=14°. Diffraction peak of 3-dimensional perovskite crystal structure was confirmed.

[Example 4]

Methylammonium bromide (CH ₃ NH ₃ Br) 0.32 mmol, lead bromide (PbBr ₂ ) 0.388 mmol, lithium bromide (LiBr ₂ ) 0.012 mmol, n-octylamine 40 μL, oleic acid 1 mL, and DMF 10 mL were mixed to prepare a solution.

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

[Example 5]

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

[Example 6]

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

[Comparative Example 1]

A solution was prepared by mixing 0.32 mmol of methylammonium bromide (CH ₃ NH ₃ Br), 0.4 mmol of lead bromide (PbBr ₂ ), 40 μL of n-octylamine, 1 mL of oleic acid and 10 mL of DMF.

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

When the X-ray diffraction pattern is measured with an X-ray diffraction measuring apparatus (XRD, CuK α line, X'pert PRO MPD, manufactured by Spectris), the X-ray diffraction pattern has a value from (hkl)=(001) at the position of 2θ=14°. Diffraction peak of 3-dimensional perovskite crystal structure was confirmed.

(Measurement of M substitution amount)

1 mL of DMF was added to 10 mL of the dispersion liquid compositions containing the compound having a perovskite crystal structure obtained in Examples 1 to 6 and Comparative Example 1 to dissolve the compound having a perovskite crystal structure. The molar numbers of M (Na or Li) and B (Pb) in the dissolved solution were measured by ICP-MS (ELAN DRCII, manufactured by Perkin Emmer), and the compounds in the compound having a perovskite crystal structure were determined. The amount of M (Na or Li) contained was evaluated by applying the formula "M/(M+Pb)".

(Measurement of quantum yield)

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, under the atmosphere), the samples containing calcium and calcium obtained in Examples 1 to 6 and Comparative Example 1 were measured. The quantum yield of the dispersion liquid composition of the compound of the titanite-type crystal structure.

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

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

The following Table 1 describes the composition and quantum yield of the dispersion liquid compositions of Examples 1 to 6 and Comparative Example 1 containing the compound having a perovskite crystal structure. In Table 1, "M/(M+Pb)" represents the molar ratio obtained by dividing the molar number of M measured by ICP-MS by the total molar number of M and B (lead ions).

From the above results, it was confirmed that the dispersion liquid compositions of Examples 1 to 6 using the present invention had good quantum yields compared to the dispersion liquid composition of Comparative Example 1 not using the present invention.

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

A glass substrate with a size of 2.5 cm×2.5 cm was prepared. This glass substrate was subjected to ozone UV treatment.

Lead bromide (PbBr ₂ ) was dissolved in a solvent of N,N-dimethylformamide (hereinafter referred to as "DMF") at 70°C to prepare a lead bromide solution having a concentration of 0.1 M. Similarly, sodium bromide (NaBr) was dissolved in a DMF solvent at 70°C to prepare a sodium bromide solution with a concentration of 0.1 M.

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

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

On the said glass substrate, the said solution was apply|coated at the rotation number of 1000 rpm by a spin coater, and it dried at 100 degreeC for 10 minutes in air|atmosphere, and obtained the coating film of a compound.

When the X-ray diffraction pattern of the compound of the coating film was measured with an X-ray diffraction measuring apparatus (XRD, CuKα ray, X'pert PRO MPD, manufactured by Spectris Corporation), there was a source from ( hkl)=(001) diffraction peak, confirming that it has a 3-dimensional perovskite crystal structure.

[Example 8]

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

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

[Example 9]

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

[Example 10]

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

[Comparative Example 2]

A glass substrate with a size of 2.5 cm×2.5 cm was prepared. This glass substrate was subjected to ozone UV treatment.

Lead bromide (PbBr ₂ ) was dissolved in a DMF solvent at 70° C. to prepare a lead bromide solution having a concentration of 0.1 M. Methylammonium bromide (CH ₃ NH ₃ Br) was dissolved in a DMF solvent at 70°C to prepare a 0.1 M concentration of methyl ammonium bromide solution.

Then, the solutions were mixed so that the molar ratio was (methylammonium bromide)/Pb=1.

On the said glass substrate, the said solution was apply|coated at the rotation number of 1000 rpm by a spin coater, and it was made to dry at 100 degreeC for 10 minutes, and the coating film of a compound was obtained.

When the X-ray diffraction pattern of the compound of the coating film was measured using an X-ray diffraction measuring apparatus (XRD, CuK α ray, X'pert PRO MPD, manufactured by Spectris), there was a source from ( hkl)=(001) diffraction peak, confirming that it has a 3-dimensional perovskite crystal structure.

(Measurement of emission spectrum)

The emission spectra of the coating films of the compounds having a perovskite crystal structure obtained in Examples 7 to 10 and Comparative Example 2 were measured using a fluorometer (manufactured by Shimadzu Corporation, trade name RF-1500, measurement conditions; excitation light 430 nm, sensitivity LOW) for measurement. Then, the transmittance (%) of the coating film at a wavelength of 430 nm was measured using an ultraviolet-visible light absorption photometer (manufactured by JASCO Corporation, trade name V-670).

In addition, the comparison of the luminous intensity between the said coating films was performed by correcting the maximum luminous intensity in the vicinity of the wavelength of 530 nm by the following formula (S)-1.

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

In the formula (S)-1, the maximum intensity near the wavelength of 530 nm refers to the emission intensity of the peak of the highest intensity confirmed between the wavelengths of 520 and 540 nm.

The following Table 2 describes the composition and maximum emission intensity of the compounds having the perovskite crystal structure of Examples 7 to 10 and Comparative Example 2. [M/(M+Pb)] in Table 2 represents a molar ratio obtained by dividing the molar number of M by the total molar number of M and B (lead ions).

From the above-mentioned results, it was confirmed that the compounds having the perovskite crystal structure of Examples 7 to 10 using the present invention had favorable properties compared to the compound having the perovskite crystal structure of Comparative Example 2 not using the present invention. light intensity.

<<Measurement by ICP-MS>>

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

According to the measurement result of ICP-MS, the value of "Na/(Pb+Na)" in Example 8 was 0.050.

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

A glass substrate with a size of 2.5 cm×2.5 cm was prepared. This glass substrate was subjected to ozone UV treatment.

Lead bromide (PbBr ₂ ) was dissolved in a solvent of N,N-dimethylformamide (hereinafter referred to as "DMF") at 70°C to prepare a lead bromide solution having a concentration of 0.1 M. Similarly, lithium bromide (LiBr) was dissolved in a DMF solvent at 70° C. to prepare a lithium bromide solution having a concentration of 0.1 M.

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

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

On the said glass substrate, the said solution was apply|coated at the rotation number of 1000 rpm by a spin coater, and it dried at 100 degreeC for 10 minutes in air|atmosphere, and obtained the coating film of a compound.

[Example 12]

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

[Example 13]

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

(Measurement of emission spectrum)

The emission spectra of the coating films of the compounds having a perovskite crystal structure obtained in Examples 11 to 13 and Comparative Example 2 were measured using a fluorometer (manufactured by Shimadzu Corporation, trade name RF-1500, measurement conditions: excitation light 430 nm, sensitivity LOW) for measurement. Then, the transmittance (%) of the coating film at a wavelength of 430 nm was measured using an ultraviolet-visible light absorption photometer (manufactured by JASCO Corporation, trade name V-670).

The comparison of the luminescence intensities between the coating films was performed by correcting the maximum luminescence intensity in the vicinity of the wavelength of 530 nm by the following formula (S)-1.

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

The following Table 3 describes the composition and the maximum emission intensity of the compounds having the perovskite crystal structure of Examples 11 to 13 and Comparative Example 2. [M/(M+Pb)] in Table 3 represents a molar ratio obtained by dividing the molar number of M calculated from the raw material feed amount by the total molar number of M and B (lead ions).

From the above results, it was confirmed that the compounds having the perovskite crystal structure of the present invention using Examples 11 to 13 of the present invention have Good luminous intensity.

(Synthesis of Compounds with Perovskite Crystal Structure) [Example 14]

A glass substrate with a size of 2.5 cm×2.5 cm was prepared. This glass substrate was subjected to ozone UV treatment.

Lead bromide (PbBr ₂ ) was dissolved in a solvent of N,N-dimethylformamide (hereinafter referred to as "DMF") at 70°C to prepare a lead bromide solution having a concentration of 0.1 M. Similarly, sodium bromide (NaBr) was dissolved in a DMF solvent at 70°C to prepare a sodium bromide solution with a concentration of 0.1 M.

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

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

On the said glass substrate, the said solution was apply|coated at the rotation number of 1000 rpm by a spin coater, and it dried at 100 degreeC for 10 minutes in air|atmosphere, and obtained the coating film of a compound.

[Example 15]

A glass substrate with a size of 2.5 cm×2.5 cm was prepared. This glass substrate was subjected to ozone UV treatment.

Lead bromide (PbBr ₂ ) was dissolved in a solvent of N,N-dimethylformamide (hereinafter referred to as "DMF") at 70°C to prepare a lead bromide solution having a concentration of 0.1 M. Similarly, sodium bromide (NaBr) was dissolved in a DMF solvent at 70°C to prepare a sodium bromide solution with a concentration of 0.1 M. Then, methylammonium iodide (CH ₃ NH ₃ I) was dissolved in a DMF solvent at 70° C. to prepare a 0.1 M concentration of methyl ammonium iodide solution. The above-mentioned lead bromide solution and sodium bromide solution were mixed so that the molar ratio [Na/(Na+Pb)] was 0.1 to prepare a solution. Then, the solution was further mixed in a molar ratio [methylammonium iodide/(Na+Pb)]=1.

On the said glass substrate, the said solution was apply|coated at the rotation number of 1000 rpm by a spin coater, and it dried at 100 degreeC for 10 minutes in air|atmosphere, and obtained the coating film of a compound.

[Example 16]

A glass substrate with a size of 2.5 cm×2.5 cm was prepared. This glass substrate was subjected to ozone UV treatment.

Lead bromide (PbBr ₂ ) was dissolved in a solvent of N,N-dimethylformamide (hereinafter referred to as "DMF") at 70°C to prepare a lead bromide solution having a concentration of 0.1 M. Similarly, lithium bromide (LiBr) was dissolved in a DMF solvent at 70° C. to prepare a lithium bromide solution having a concentration of 0.1 M. Then, methylammonium chloride (CH ₃ NH ₃ Cl) was dissolved in a DMF solvent at 70° C. to prepare a 0.1 M concentration of methyl ammonium chloride solution. The above-mentioned lead bromide solution and lithium bromide solution were mixed in a molar ratio [Li/Li+Pb]=0.1. Then, the solution was further mixed in a molar ratio [methylammonium chloride/Li+Pb]=1.

On the said glass substrate, the said solution was apply|coated at the rotation number of 1000 rpm by a spin coater, and it dried at 100 degreeC for 10 minutes in air|atmosphere, and obtained the coating film of a compound.

[Example 17]

A glass substrate with a size of 2.5 cm×2.5 cm was prepared. This glass substrate was subjected to ozone UV treatment.

Lead bromide (PbBr ₂ ) was dissolved in a solvent of N,N-dimethylformamide (hereinafter referred to as "DMF") at 70°C to prepare a lead bromide solution having a concentration of 0.1 M. Similarly, lithium bromide (LiBr) was dissolved in a DMF solvent at 70° C. to prepare a lithium bromide solution having a concentration of 0.1 M. Then, methylammonium iodide (CH ₃ NH ₃ I) was dissolved in a DMF solvent at 70° C. to prepare a 0.1 M concentration of methyl ammonium iodide solution. The above-mentioned lead bromide solution and lithium bromide solution were mixed so that the molar ratio [Li/(Li+Pb)] was 0.1 to prepare a solution. Then, the solution was further mixed in a molar ratio [methylammonium iodide/(Li+Pb)]=1.

On the said glass substrate, the said solution was apply|coated at the rotation number of 1000 rpm by a spin coater, and it dried at 100 degreeC for 10 minutes in air|atmosphere, and obtained the coating film of a compound.

[Comparative Example 3]

A glass substrate with a size of 2.5 cm×2.5 cm was prepared. This glass substrate was subjected to ozone UV treatment.

Lead bromide (PbBr ₂ ) was dissolved in a solvent of N,N-dimethylformamide (hereinafter referred to as "DMF") at 70°C to prepare a lead bromide solution having a concentration of 0.1 M. Then, methylammonium chloride (CH ₃ NH ₃ Cl) was dissolved in a DMF solvent at 70° C. to prepare a 0.1 M concentration of methyl ammonium chloride solution.

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

On the said glass substrate, the said solution was apply|coated at the rotation number of 1000 rpm by a spin coater, and it dried at 100 degreeC for 10 minutes in air|atmosphere, and obtained the coating film of a compound.

[Comparative Example 4]

A glass substrate with a size of 2.5 cm×2.5 cm was prepared. This glass substrate was subjected to ozone UV treatment.

Lead bromide (PbBr ₂ ) was dissolved in a solvent of N,N-dimethylformamide (hereinafter referred to as "DMF") at 70°C to prepare a lead bromide solution having a concentration of 0.1 M. Then, methylammonium iodide (CH ₃ NH ₃ I) was dissolved in a DMF solvent at 70° C. to prepare a 0.1 M concentration of methyl ammonium iodide solution.

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

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

(Measurement of emission spectrum)

The emission spectra of the coating films of the compounds having the perovskite crystal structure obtained in Examples 14, 16 and Comparative Example 3 were measured using a fluorophotometer (manufactured by JASCO Corporation, trade name FT-6500, measurement conditions: excitation light 430 nm, high sensitivity) for measurement. Then, the transmittance (%) at 430 nm of the coating film was measured using an ultraviolet-visible light absorption photometer (manufactured by JASCO Corporation, trade name V-670).

The comparison of the luminescence intensities between the coating films was performed by correcting the maximum luminescence intensity in the vicinity of the wavelength of 500 nm by the following formula (S)-2.

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

In Formula (S)-2, the maximum intensity near a wavelength of 500 nm refers to the emission intensity of the peak of the highest intensity confirmed between wavelengths 490 to 510 nm.

(Measurement of emission spectrum)

The emission spectra of the coating films of the compounds having the perovskite crystal structure obtained in Examples 15, 17 and Comparative Example 4 were measured using a fluorophotometer (manufactured by JASCO Corporation, trade name FT-6500, measurement conditions: excitation light 430 nm, high sensitivity) for measurement. Then, the transmittance (%) at 430 nm of the coating film was measured using an ultraviolet-visible light absorption photometer (manufactured by JASCO Corporation, trade name V-670).

The comparison of the luminescence intensities between the coating films was performed by correcting the maximum luminescence intensity in the vicinity of the wavelength of 540 nm by the following formula (S)-3.

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

In the formula (S)-3, the maximum intensity near the wavelength of 540 nm refers to the emission intensity of the peak of the highest intensity confirmed between the wavelengths of 530 and 550 nm.

The following Table 4 describes the composition and maximum emission intensity of the compounds having the perovskite crystal structure of Examples 14 to 17 and Comparative Examples 3 to 4. In Table 4, "M/(M+Pb)" represents the molar ratio obtained by dividing the molar number of M calculated from the raw material feed amount by the total molar number of M and B (lead ions).

From the above results, it was confirmed that the compounds having the perovskite-type crystal structure of Examples 14 to 17 of the present invention had Good luminous intensity.

[Example 18]

10 mL of DMF was added and mixed to cesium bromide (CsBr) so that the concentration of cesium would be 2700 ppm (μg/g). A solution was prepared by mixing 0.38 mmol of lead bromide (PbBr ₂ ), 0.02 mmol of sodium bromide (NaBr), 88 μL of n-octylamine, 1 mL of oleic acid, and the above-mentioned cesium bromide solution.

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

[Comparative Example 5]

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

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

(Measurement of M substitution amount)

To 10 mL of the dispersion liquid composition containing the compound having a perovskite crystal structure obtained in Example 18, 1 mL of DMF was added to dissolve the compound having a perovskite crystal structure. The molar numbers of M (Na) and B (Pb) in the dissolved solution were measured by ICP-MS (ELAN DRCII, manufactured by Perkin Emmer), and the compounds having a perovskite crystal structure contained in the The amount of M(Na) of , was evaluated using the formula "M/(M+Pb)".

(Measurement of quantum yield)

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

(Determination of perovskite compounds)

The concentrations of the perovskite compounds of the compositions obtained in Example 18 and Comparative Example 5 were respectively added to the dispersions containing the perovskite compounds and the solvent by adding N,N-dimethylformamide to make the perovskite compounds. After the compound of the type was dissolved, it was measured using ICP-MS (ELAN DRCII, manufactured by Perkin Emmer) and an ion chromatography.

The following Table 5 describes the composition and quantum yield of the compounds having the perovskite crystal structure of Example 18 and Comparative Example 5. In Table 5, [M/(M+Pb)] represents the molar ratio obtained by dividing the molar number of M by the total molar number of M and B (lead ions).

From the above-mentioned results, it was confirmed that the present invention using Example 18 of the present invention contained a compound having a perovskite-type crystal structure compared to the dispersion liquid composition containing a compound having a perovskite-type crystal structure in Comparative Example 5 not using the present invention. The dispersion liquid composition of the compound of the crystalline structure has a good quantum yield.

[Reference Example 1]

The dispersion liquid composition of the present invention described in Examples 1 to 6 is mixed with the resin, and the liquid is removed to obtain the resin composition of the present invention, which is placed in a glass tube, etc., sealed, and then placed in a blue light source. Between the light-emitting diode and the light guide plate, a backlight that can convert the blue light of the blue light-emitting diode into green light and red light is manufactured.

[Reference Example 2]

After mixing the dispersion composition described in Examples 1 to 6 with the resin, removing the liquid and forming a sheet, the resin composition of the present invention can be obtained, which is sandwiched and sealed with two barrier films and placed on a light guide plate, The blue light emitting diode placed on the end surface (side surface) of the light guide plate and the blue light irradiated on the sheet through the light guide plate can be converted into green light and red light.

[Reference Example 3]

After mixing the dispersion composition of the present invention described in Examples 1 to 6 with the resin, and removing the solvent, the resin composition of the present invention can be obtained. The blue light is converted into green light and red light for the backlight.

[Reference Example 4]

After mixing the dispersion liquid compositions of the present invention described in Examples 1 to 6 with a photoresist, the solvent is removed to obtain a wavelength conversion material. The obtained wavelength conversion material is arranged between the blue light-emitting diode of the light source and the light guide plate, or the back stage of the OLED of the light source, to manufacture a backlight that can convert blue light of the light source into green light and red light.

[Reference Example 5]

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

[Reference Example 6]

On the surface of a fluorine-doped tin oxide (FTO) substrate, a dense layer of titanium oxide is layered, a porous alumina layer is layered thereon, and a perovskite layer is layered thereon using the dispersion compositions described in Examples 1 to 6. The ore layer, and 2,2',7,7'-tetrakis(N,N'-di-p-methoxyphenylamine)-9,9'-spiro-OMeTAD, etc. The hole transport layer is then laminated with a silver (Ag) layer thereon to form a solar cell.

[Reference Example 7]

After mixing the dispersion liquid composition containing the compound having the perovskite crystal structure of the present invention described in Examples 1 to 6 with a resin, and then removing the solvent and molding, the composition containing the perovskite crystal structure of the present invention can be obtained. When the resin composition of the compound is provided in the latter stage of the blue light-emitting diode, the blue light irradiated on the resin molded body from the blue light-emitting diode is converted into green light and red light and emits white light. Laser diode lighting.

[Industrial Availability]

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

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

The present invention discloses a compound and a composition comprising the compound, and the drawings in this specification are only the structure of a laminate and a liquid crystal display using the composition of the present invention, and cannot be used as representative drawings of the present invention, so there is no designation in this case. Representative figure.

Claims (9)

A composition comprising a compound having a perovskite crystal structure, the compound is composed of A, B, X and M, and the molar ratio of the molar number of M divided by the total molar number of M and B is obtained The value of [M/ _{( M +} B ₎ ] is not less than 0.01 and not more than 0.7 _{; a} X _(4+δ) represents at least any one; A represents the component located at each vertex of the hexahedron centered on B, X represents the component located at each vertex of the octahedron centered on B, A represents the component located at each vertex of the hexahedron centered on B is the cesium ion, organic ammonium ion or amidinium ion located at each vertex of the hexahedron with B as the center in the aforementioned perovskite crystal structure; B is lead ion; M is sodium ion or lithium ion, and M is at least A part replaces a part of B in the aforementioned perovskite crystal structure; X represents a component located at each vertex of the octahedron with B as the center in the aforementioned perovskite crystal structure, which is selected from chloride ions, bromine One or more anions of the group consisting of compound ion, fluoride ion, iodide ion and thiocyanate ion; a represents the molar ratio obtained by dividing the number of moles of M by the total number of moles of M and B [ M/(M+B)]; δ is 0 or more and 0.7 or less. The composition according to claim 1, wherein the A is an organic ammonium ion. The composition described in item 1 or 2 of the scope of the application, which is described in the above The composition contains a liquid as a medium. The composition as described in claim 1 or 2 of the claimed scope, which comprises a resin as a medium in the aforementioned composition. A compound having a perovskite crystal structure, which is a molar ratio [M/( The value of M+B)] is 0.01 or more and 0.7 or less; the aforementioned perovskite crystal structure is composed of AB _(1-a) M _a X _(3+δ) and A ₂ B _(1-a) M _a X _{(4 +δ)} is represented by at least one of them; A represents the component located at each vertex of the hexahedron centered on B, X represents the component located at each vertex of the octahedron centered on B; A represents the component located on the aforementioned Cesium ion, organic ammonium ion or amidinium ion at each vertex of the hexahedron with B as the center in the perovskite crystal structure; B is lead ion; M is sodium ion or lithium ion, and at least a part of M is in the aforementioned calcium ion. A part of B is substituted in the titanite-type crystal structure; X represents the component located at each vertex of the octahedron with B as the center in the aforementioned perovskite-type crystal structure, which is selected from chloride ions, bromide ions, fluorine ions One or more anions of the group consisting of compound ion, iodide ion and thiocyanate ion; a represents the molar ratio of M divided by the total molar number of M and B [M/(M +B)]; δ is 0 or more and 0.7 or less. A film comprising the composition or the application described in item 4 of the scope of the patent application. Please refer to the compound described in item 5 of the patent scope. A layered structure having a layer including the composition described in claim 4 or the compound described in claim 5. A light-emitting device including the laminated structure described in claim 7 and a light source. A liquid crystal display comprising: the light-emitting device and the liquid crystal panel described in claim 8 of the scope of application.

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