CN113784925B

CN113784925B - Compound, composition, film, laminated structure, light-emitting device, display, and method for producing compound

Info

Publication number: CN113784925B
Application number: CN202080032179.2A
Authority: CN
Inventors: 内藤翔太; 杉内瑞穗; 有村孝
Original assignee: Sumitomo Chemical Co Ltd
Current assignee: Sumitomo Chemical Co Ltd
Priority date: 2019-03-01
Filing date: 2020-02-26
Publication date: 2023-11-03
Anticipated expiration: 2040-02-26
Also published as: CN113784925A; WO2020179579A1; JP7470532B2; TW202039792A; JP2020142981A

Abstract

A compound (1) having a perovskite crystal structure, wherein the half width of the peak of the Miller index (001) is 0.10 or more and less than 0.60 in an X-ray diffraction pattern, and wherein the compound comprises a 1-valent cation A, a metal ion B, and an anion X of at least one selected from the group consisting of a halide ion and a thiocyanate ion as constituent components.

Description

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

Technical Field

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

Background

As a light-emitting material, a light-emitting semiconductor compound has been attracting attention. In order to produce a light-emitting material having high color purity, a light-emitting semiconductor compound is required to have a sharp emission peak narrower than the half width of its emission spectrum.

Prior art literature

Non-patent literature

[ non-patent document 1 ] Advanced Materials 2016,28, p.10088-10094

Disclosure of Invention

Problems to be solved by the invention

As the above-mentioned luminescent semiconductor compound, for example, a compound having a perovskite crystal structure is reported (non-patent document 1). However, the compound having a perovskite crystal structure described in non-patent document 1 has a broad half-width of the emission spectrum, and it is difficult to expect an improvement in color purity.

The present invention has been made in view of the above problems, and an object thereof is to provide: a compound having a perovskite crystal structure, a composition containing the compound, a thin film containing the composition as a forming material, a laminated structure containing the thin film, a light-emitting device having the laminated structure, a display, and a method for producing the compound, wherein the half width of the light-emitting spectrum is narrow.

Means for solving the problems

In order to solve the above problems, the present inventors have focused on studies and as a result have obtained the following invention.

The present invention includes the following [1] to [10].

[1] A compound having a perovskite crystal structure composed of A, B and X as constituent components, wherein the half width of the peak of the Miller index (001) is 0.10 or more and less than 0.60 in an X-ray diffraction pattern.

(A is a component located at each vertex of the 6-plane body centering around B in the perovskite crystal structure, and is a 1-valent cation.

X is a component located at each vertex of the 8-plane body centering around B in the perovskite crystal structure, and is an anion selected from at least one of the group consisting of halide ions and thiocyanate ions.

B is a component located at the center of 6-plane bodies arranged at the apex of a and 8-plane bodies arranged at the apex of X in the perovskite crystal structure, and is a metal ion. )

[2] A composition comprising: the compound according to claim 1, wherein the compound is at least one selected from the group consisting of (2-1) below, a modified product of (2-1) below, and a modified product of (2-2) below and (2-2) below.

(2-1) silazanes

(2-2) a silicon compound having at least one group selected from the group consisting of an amino group, an alkoxy group and an alkylthio group

[3] A composition comprising: [1] the compound, and at least one selected from the group consisting of the following (3), the following (4) and the following (5).

(3) Solvent(s)

(4) Polymerizable compound

(5) Polymer

[4] The composition according to [2], which further comprises at least one selected from the group consisting of the following (3), the following (4) and the following (5).

(3) Solvent(s)

(4) Polymerizable compound

(5) Polymer

[5] A film comprising the compound according to [1 ].

[6] A film comprising the composition of any one of [2] to [4] as a forming material.

[7] A laminated structure comprising the film of [5] or [6 ].

[8] A light-emitting device comprising the laminated structure of [7 ].

[9] A display comprising the laminated structure of [7 ].

[10]A method of manufacturing a semiconductor compound, comprising: a step of mixing a raw material containing either or both of a simple substance of a metal element M and a compound containing the metal element M with water; and a step of reacting the raw materials in the presence of the water; mass W of the water _W W relative to the mass of the metal element M contained in the raw material _M Ratio (W) _W /W _M ) 0.05 to 100, wherein the semiconductor compound contains a metal element M and has a half width of a peak of a crystal face Miller index (001) of 0.10 or more in an X-ray diffraction patternLess than 0.60.

Effects of the invention

According to the present invention, a compound having a perovskite crystal structure with a narrow half width of an emission spectrum, a composition containing the compound, a thin film using the composition as a forming material, a laminated structure containing the thin film, a light-emitting device and a display each including the laminated structure can be provided.

Further, according to the present invention, a method for producing a compound having a narrow half width of an emission spectrum can be provided.

Drawings

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

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

Symbol description

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

Detailed Description

Hereinafter, the present invention will be described in detail with reference to the embodiments.

< Compound having perovskite Crystal Structure >

The compound of the present embodiment is a compound having a perovskite crystal structure (hereinafter also referred to as a "(1) perovskite compound", or simply referred to as a "(1)") having A, B and X as constituent components.

A is a component located at each vertex of a hexahedron centered on B in the perovskite crystal structure, and is a 1-valent cation.

B is a component located in the center of a hexahedron arranged at the apex of a and an octahedron arranged at the apex of X in the perovskite crystal structure, and is a metal ion. B is a metal cation which can form octahedral coordination with X.

X is a component located at each vertex of an octahedron centered on B in the perovskite crystal structure, and is an anion selected from at least one of the group consisting of halide ions and thiocyanate ions.

The structure of the perovskite compound having A, B and X as constituent components may be any one of a three-dimensional structure, a two-dimensional structure, and a quasi two-dimensional (quasi-2D) structure.

In the case of three-dimensional structure, the perovskite compound has a composition formula of ABX _(3+δ) And (3) representing.

In the case of a two-dimensional structure, the perovskite compound has the composition formula A ₂ BX _(4+δ) And (3) representing.

Here, δ is a value which can be changed appropriately according to the charge balance of B, and is-0.7 or more and 0.7 or less. For example, when A is a 1-valent cation, B is a 2-valent cation, and X is a 1-valent anion, δ may be selected so that the perovskite compound is electrically neutral. The perovskite compound being electrically neutral means that the charge of the perovskite compound is 0.

The perovskite compound contains an octahedron with B as a center and X as a vertex. Octahedron with BX ₆ And (3) representing.

When the perovskite compound has a three-dimensional structure, BX contained in the perovskite compound ₆ By making octahedron (BX ₆ ) Is positioned at the vertex of one X, is divided by two adjacent octahedrons (BX ₆ ) And sharing, thereby forming a three-dimensional network.

When the perovskite compound has a two-dimensional structure, BX contained in the perovskite compound ₆ By making octahedron (BX ₆ ) Is positioned at the vertex of two X, is divided by two adjacent octahedrons (BX ₆ ) And sharing, namely, sharing the edge lines of the octahedron and two-dimensionally connected layers. Perovskite compounds have BX linked by two dimensions ₆ The layers of the structure are alternately laminated with the layers of A.

In the present specification, the crystal structure of the perovskite compound can be confirmed by an X-ray diffraction pattern (hereinafter, also referred to as XRD). Further, the respective crystal distributions of the perovskite compounds in the aggregate of the perovskite compounds composed of the plurality of perovskite compounds can also be confirmed by XRD.

When the perovskite compound has a perovskite crystal structure having a three-dimensional structure, a peak derived from (hkl) = (001) is usually observed in the position where the crystal face miller index (hkl) of the perovskite compound is 2θ=12 to 18 ° in the X-ray diffraction pattern. Alternatively, a peak derived from (hkl) = (110) can be confirmed at a position of 2θ=18 to 25 °.

When the perovskite compound has a perovskite crystal structure having a three-dimensional structure, in general, in an X-ray diffraction pattern, a peak derived from (hkl) = (001) is confirmed at a position where the crystal face miller index (hkl) of the perovskite compound is 2θ=13 to 16 °, or, preferably, a peak derived from (hkl) = (110) is confirmed at a position where 2θ=20 to 23 °.

When the perovskite compound has a perovskite crystal structure having a two-dimensional structure, a peak derived from (hkl) = (002) is usually observed in the X-ray diffraction pattern at a position where the crystal face miller index (hkl) of the perovskite compound is 2θ=1 to 10 °. It is preferable that a peak derived from (hkl) = (002) is confirmed at a position of 2θ=2 to 8 °.

The perovskite compound preferably has a three-dimensional structure.

In the X-ray diffraction pattern measured by XRD, the half width of the peak of (hkl) = (001) of the perovskite compound (1) of the present embodiment is 0.10 (deg) or more and less than 0.60 (deg). The half width is preferably 0.15 (deg) or more and 0.50 (deg) or less, preferably 0.20 (deg) or more and 0.30 (deg) or less, preferably 0.15 (deg) or more and 0.28 (deg) or less, preferably 0.20 (deg) or more and 0.25 (deg) or less.

In another aspect of this embodiment, the half width of the peak of (hkl) = (001) of the (1) perovskite compound is 0.10, 0.11, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, 0.20, 0.21, 0.22, 0.23, 0.24, 0.25, 0.26, 0.27, 0.28, 0.29, 0.30, 0.35, 0.40, 0.45, 0.50, 0.55 (deg) or more.

In another aspect of this embodiment, the half width of the peak of (hkl) = (001) of the (1) perovskite compound is 0.15, 0.16, 0.17, 0.18, 0.19, 0.20, 0.21, 0.22, 0.23, 0.24, 0.25, 0.26, 0.27, 0.28, 0.29, 0.30, 0.31, 0.32, 0.33, 0.34, 0.35, 0.36, 0.37, 0.38, 0.39, 0.40, 0.41, 0.42, 0.43, 0.44, 0.45, 0.46, 0.47, 0.48, 0.49, 0.50, 0.51, 0.52, 0.53, 0.54, 0.55, 0.56, 0.57, 0.58, 0.59 (deg) or less.

If the half width of the peak of (hkl) = (001) of (1) the perovskite compound is 0.15 or more, crystals of the perovskite compound can be stably formed. Further, when the half width of the peak is 0.20 or more, the above effect is obtained and the excitation light absorptance is improved.

If the half width of the peak of (hkl) = (001) of (1) the perovskite compound is smaller than 0.60, the half width of the emission wavelength becomes narrow.

(1) The half width of (hkl) = (001) of the perovskite compound can be calculated using X-ray powder diffraction integrated analysis software PDXL (manufactured by Rigaku Corporation) using an XRD spectrum (cukα ray).

The half width of (hkl) = (001) of the perovskite compound of the present embodiment and the semiconductor compound produced by the production method described later can be specifically confirmed as follows.

0.05mL of a dispersion composition containing the perovskite compound of the present embodiment or the semiconductor compound produced by a production method described later was dropped onto the washed reflection-free plate, and the resultant was naturally dried. Powder X-ray diffraction measurement was performed with CuKα as a radiation source and with a diffraction angle 2 theta in a measurement range of 5 DEG to 60 DEG inclusive, and a peak corresponding to (hkl) = (001) was determined. Further, using the above analysis software, the half width of the determined (hkl) = (001) was calculated.

(constituent A)

A constituting the perovskite compound is a 1-valent cation. Examples of A include cesium ions, organic ammonium ions and amidinium ions.

(organic ammonium ion)

The organic ammonium ion of a specifically includes a cation represented by the following formula (A3).

[ chemical formula 1 ]

In the formula (A3), R ⁶ ～R ⁹ Each independently represents a hydrogen atom, an alkyl group or a cycloalkyl group. Wherein R is ⁶ ～R ⁹ At least one of which is alkyl or cycloalkyl, R ⁶ ～R ⁹ And are not hydrogen atoms at the same time.

R ⁶ ～R ⁹ The alkyl group may be linear or branched. In addition, R ⁶ ～R ⁹ The alkyl groups shown may each independently have an amino group as a substituent.

In one embodiment, R ⁶ ～R ⁹ The number of carbon atoms of the alkyl group is usually 1 to 20, preferably 1 to 4, more preferably 1 to 3, and still more preferably 1, independently of each other.

In one embodiment, R ⁶ ～R ⁹ The number of carbon atoms of the alkyl group is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or more independently. In other modes, R ⁶ ～R ⁹ The number of carbon atoms of the alkyl group is 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2 or less, respectively.

R ⁶ ～R ⁹ The cycloalkyl groups shown may each independently have an amino group as a substituent.

In one embodiment, R ⁶ ～R ⁹ The number of carbon atoms of the cycloalkyl group is usually 3 to 30, preferably 3 to 11, more preferably 3 to 8, independently of each other. The number of carbon atoms includes the number of carbon atoms of the substituent.

In one embodiment, R ⁶ ～R ⁹ The number of carbon atoms of the cycloalkyl group is 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29 or more, respectively. In other modes, R ⁶ ～R ⁹ The number of carbon atoms of the cycloalkyl group is 30, 29, 28, 27, 26, 25, 24, 23, 22, 21, 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, or 4 or less, respectively.

In one embodiment, R is ⁶ ～R ⁹ The radicals shown are each independently preferably a hydrogen atom or an alkyl radical.

When the perovskite compound A contains an organic ammonium ion represented by the above formula (A3), the smaller the number of alkyl groups and cycloalkyl groups that the formula (A3) can contain, the better. In addition, the smaller the number of carbon atoms of the alkyl group and cycloalkyl group which the formula (A3) may contain, the better. Thus, a perovskite compound having a three-dimensional structure with high luminous intensity can be obtained.

Among the organic ammonium ions represented by the formula (A3), R is preferable ⁶ ～R ⁹ The total number of carbon atoms contained in the alkyl group and cycloalkyl group is 1 to 4.

In addition, among the organic ammonium ions represented by the formula (A3), R is more preferable ⁶ ～R ⁹ One of them is C1-3 alkyl, R ⁶ ～R ⁹ Three of which are hydrogen atoms.

As R ⁶ ～R ⁹ Examples of the alkyl group include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, 1-methylbutyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, 2-dimethylbutyl, 2, 3-dimethylbutyl, n-heptyl, 2-methylhexyl, 3-methylhexyl, 2-dimethylpentyl, 2, 3-dimethylpentyl, 2, 4-dimethylpentyl, 3-dimethylpentyl, 3-ethylpentyl, 2, 3-trimethylbutyl, n-octyl, isooctyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, and eicosyl groups.

As R ⁶ ～R ⁹ Cycloalkyl groups of (2) are each independently exemplified as R ⁶ ～R ⁹ The alkyl group having 3 or more carbon atoms is exemplified as the alkyl group. Examples thereof include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, norbornyl, isobornyl, 1-adamantyl, 2-adamantyl, and tricyclodecyl.

In one embodiment, the organic ammonium represented by A is dissociatedSon, preferably CH ₃ NH ₃ ⁺ (also known as methylamine ions), C ₂ H ₅ NH ₃ ⁺ (also known as ethylammonium ions) or C ₃ H ₇ NH ₃ ⁺ (also referred to as a propylammonium ion), more preferably a methylammonium ion or an ethylammonium ion, still more preferably a methylammonium ion.

(amidinium ion)

In one embodiment, the amidinium ion represented by A is, for example, an amidinium ion represented by the following formula (A4).

(R ¹⁰ R ¹¹ N＝CH-NR ¹² R ¹³ ) ⁺ ···(A4)

In the formula (A4), R ¹⁰ ～R ¹³ Each independently represents a hydrogen atom, an alkyl group or a cycloalkyl group.

R ¹⁰ ～R ¹³ The alkyl groups may be linear or branched, independently. In addition, R ¹⁰ ～R ¹³ The alkyl groups shown may each independently have an amino group as a substituent.

In one embodiment, R ¹⁰ ～R ¹³ The number of carbon atoms of the alkyl group is usually 1 to 20, preferably 1 to 4, more preferably 1 to 3, independently of each other. In one embodiment, R ¹⁰ ～R ¹³ The number of carbon atoms of the alkyl group is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or more independently. In other modes, R ¹⁰ ～R ¹³ The number of carbon atoms of the alkyl group is 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2 or less, respectively.

R ¹⁰ ～R ¹³ The cycloalkyl groups shown may each independently have an amino group as a substituent.

In one embodiment, R ¹⁰ ～R ¹³ The number of carbon atoms of the cycloalkyl group is usually 3 to 30, preferably 3 to 11, more preferably 3 to 8, independently of each other. The number of carbon atoms includes the number of carbon atoms of the substituent.

In one embodiment, R ¹⁰ ～R ¹³ The number of carbon atoms of the cycloalkyl group shownEach independently is 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29 or more. In other modes, R ¹⁰ ～R ¹³ The number of carbon atoms of the cycloalkyl group is 30, 29, 28, 27, 26, 25, 24, 23, 22, 21, 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, or 4 or less, respectively.

As R ¹⁰ ～R ¹³ Specific examples of the alkyl group of (2) are, independently of each other, R ⁶ ～R ⁹ The same groups as those exemplified for the alkyl groups.

As R ¹⁰ ～R ¹³ Specific examples of cycloalkyl groups of (2) are, independently of each other, R ⁶ ～R ⁹ Cycloalkyl groups as exemplified in (a) are the same groups as those exemplified in (b).

In one embodiment, R is ¹⁰ ～R ¹³ The radicals shown are each independently preferably hydrogen atoms or alkyl radicals.

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

In one embodiment, R is preferably selected from among the amidinium ions ¹⁰ ～R ¹³ The total number of carbon atoms contained in the alkyl and cycloalkyl groups shown is 1 to 4, more preferably R ¹⁰ Is C1 alkyl, R ¹¹ ～R ¹³ Is a hydrogen atom.

In the perovskite compound, when a is cesium ion, an organic ammonium ion having 3 or less carbon atoms, or an amidinium ion having 3 or less carbon atoms, the perovskite compound generally has a three-dimensional structure.

In the perovskite compound, when a is an organic ammonium ion having 4 or more carbon atoms or an amidinium ion having 4 or more carbon atoms, the perovskite compound has either one or both of a two-dimensional structure and a quasi-two-dimensional (quasi-2D) structure. At this time, a part or all of the crystals of the perovskite compound may have a two-dimensional structure or a quasi-two-dimensional structure.

When a plurality of two-dimensional perovskite crystal structures are laminated, they are equivalent to three-dimensional perovskite crystal structures (references: P.PBoix et al, J.Phys.chem. Lett.2015,6,898-907, etc.).

In one embodiment, a in the perovskite compound is preferably cesium ion or amidinium ion, more preferably amidinium ion.

(1) In the perovskite compound, a may be used alone or in combination of two or more.

(constituent component B)

The B constituting the perovskite compound may be 1 or more metal ions selected from the group consisting of 1-valent metal ions, 2-valent metal ions, and 3-valent metal ions. In one embodiment, B preferably contains a 2-valent metal ion, more preferably contains 1 or more metal ions selected from the group consisting of lead ion, tin ion, antimony ion, bismuth ion, and indium ion, further preferably is lead ion or tin ion, and particularly preferably is lead ion.

(1) In the perovskite compound, B may be used alone or in combination of two or more.

(constituent X)

X constituting the perovskite compound may be an anion of at least one selected from the group consisting of a halide ion and a thiocyanate ion.

Examples of the halogen ion include chloride ion, bromide ion, fluoride ion, and iodide ion. X is preferably a bromide ion.

(1) In the perovskite compound, X may be used alone or in combination of two or more.

When X contains two or more kinds of halide ions, the content ratio of the halide ions can be appropriately selected according to the emission wavelength. For example, a combination of bromide and chloride, or a combination of bromide and iodide.

X may be appropriately selected according to a desired emission wavelength.

In one embodiment, the perovskite compound in which X is a bromide ion emits fluorescence having a maximum intensity peak in a wavelength range of usually 480nm or more, preferably 500nm or more, more preferably 520nm or more.

In other embodiments, the perovskite compound in which X is a bromide ion may emit fluorescence having a peak with a maximum intensity in a wavelength range of 480, 490, 500, 510, 520, 530, 540, 550, 560, 570, 580, 590, 600, 610, 620, 630, 640, 650, 660, 670, 680, 690nm or more.

In one embodiment, the perovskite compound in which X is a bromide ion emits fluorescence having a maximum intensity peak in a wavelength range of usually 700nm or less, preferably 600nm or less, more preferably 580nm or less.

In other embodiments, the perovskite compound in which X is a bromide ion may emit fluorescence having a peak with a maximum intensity in a wavelength range of 700, 690, 680, 670, 660, 650, 640, 630, 620, 600, 590, 580, 570, 560, 550, 540, 530, 520, 510nm or less.

The upper limit value and the lower limit value of the above wavelength range may be arbitrarily combined.

In one embodiment, when X in the perovskite compound is a bromide ion, the peak of fluorescence emitted is usually 480 to 700nm, preferably 500 to 600nm, more preferably 520 to 580nm.

In one embodiment, the perovskite compound in which X is an iodide ion emits fluorescence having a maximum intensity peak in a wavelength range of usually 520nm or more, preferably 530nm or more, more preferably 540nm or more.

In other embodiments, the perovskite compound in which X is an iodide ion may emit fluorescence having a peak with a maximum intensity in a wavelength range of 520, 530, 540, 550, 560, 570, 580, 590, 600, 610, 620, 630, 640, 650, 660, 670, 680, 690, 700, 710, 720, 730, 740, 750, 760, 770, 780, 790nm or more.

In one embodiment, the perovskite compound in which X is an iodide ion emits fluorescence having a maximum intensity peak in a wavelength range of usually 800nm or less, preferably 750nm or less, more preferably 730nm or less.

In other embodiments, perovskite compounds in which X is iodide may emit fluorescence having a maximum intensity peak in a wavelength range of 800, 790, 780, 770, 760, 750, 740, 730, 720, 710, 700, 690, 680, 670, 660, 650, 640, 630, 620, 600, 590, 580, 570, 560, 550, 540nm or less.

In one embodiment, when X in the perovskite compound is iodide ion, the peak of fluorescence emitted is usually 520 to 800nm, preferably 530 to 750nm, and more preferably 540 to 730nm.

In one embodiment, the perovskite compound in which X is a chloride ion emits fluorescence having a maximum intensity peak in a wavelength range of usually 300nm or more, preferably 310nm or more, more preferably 330nm or more.

In other embodiments, the perovskite compound in which X is chloride may emit fluorescence having a peak with a maximum intensity in a wavelength range of 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400, 410, 420, 430, 440, 450, 460, 470, 480, 490, 500, 510, 520, 530, 540, 550, 560, 570, 580, 590nm or more.

In one embodiment, the perovskite compound in which X is a chloride ion emits fluorescence having a maximum intensity peak in a wavelength range of usually 600nm or less, preferably 580nm or less, more preferably 550nm or less.

In other embodiments, perovskite compounds in which X is chloride may emit fluorescence having a peak of maximum intensity in a wavelength range of 600, 590, 580, 570, 560, 550, 540, 530, 520, 510, 500, 490, 480, 470, 460, 450, 440, 430, 420, 410, 400, 390, 380, 370, 360, 350, 340, 330, 320, 310nm or less.

In one embodiment, when X in the perovskite compound is chloride ion, the peak of fluorescence emitted is usually 300 to 600nm, preferably 310 to 580nm, and more preferably 330 to 550nm.

(illustration of perovskite Compound of three-dimensional Structure)

As ABX _(3+δ) Preferred examples of the perovskite compound having a three-dimensional structure include CH ₃ NH ₃ PbBr ₃ 、CH ₃ NH ₃ PbCl ₃ 、CH ₃ NH ₃ PbI ₃ 、CH ₃ NH ₃ PbBr _(3-y) I _y (0＜y＜3)、CH ₃ NH ₃ PbBr _(3-y) Cl _y (0＜y＜3)、(H ₂ N＝CH-NH ₂ )PbBr ₃ 、(H ₂ N＝CH-NH ₂ )PbCl ₃ 、(H ₂ N＝CH-NH ₂ )PbI ₃ But is not limited thereto.

As a preferred example of the perovskite compound having a three-dimensional structure, CH may be mentioned ₃ NH ₃ Pb _(1-a) Ca _a Br ₃ (0＜a≤0.7)、CH ₃ NH ₃ Pb _(1-a) Sr _a Br ₃ (0＜a≤0.7)、CH ₃ NH ₃ Pb _(1-a) La _a Br _(3+δ) (0＜a≤0.7，0＜δ≤0.7)、CH ₃ NH ₃ Pb _(1-a) Ba _a Br ₃ (0＜a≤0.7)、CH ₃ NH ₃ Pb _(1-a) Dy _a Br _(3+δ) (0 < a.ltoreq. 0.7,0 < δ.ltoreq.0.7), but is not limited thereto.

As a preferred example of the perovskite compound having a three-dimensional structure, CH may be mentioned 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.ltoreq.0.7, -0.7.ltoreq.delta.ltoreq.0), but is not limited thereto.

As a preferred example of the perovskite compound having a three-dimensional structure, csPb may be mentioned _(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.ltoreq.0.7, -0.7.ltoreq.delta.ltoreq.0), but is not limited thereto.

As a preferred example of the perovskite compound having a three-dimensional structure, CH may be mentioned 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.ltoreq.0.7, -0.7.ltoreq.delta.ltoreq.0, 0 < y < 3), but is not limited thereto.

Preferred examples of the perovskite compound having a three-dimensional structure include (H ₂ N＝CH-NH ₂ )Pb _(1-a) Na _a Br _(3+δ) (0＜a≤0.7，-0.7≤δ＜0)、(H ₂ N＝CH-NH ₂ )Pb _(1-a) Li _a Br _(3+δ) (0＜a≤0.7，-0.7≤δ＜0)、(H ₂ N＝CH-NH ₂ )Pb _(1-a) Na _a Br _(3+δ-y) I _y (0＜a≤0.7，-0.7≤δ＜0，0＜y＜3)、(H ₂ N＝CH-NH ₂ )Pb _(1-a) Na _a Br _(3+δ-y) Cl _y (0 < a.ltoreq.0.7, -0.7.ltoreq.delta.ltoreq.0, 0 < y < 3), but is not limited thereto.

As a preferred example of the perovskite compound having a three-dimensional structure, csPbBr may be mentioned ₃ 、CsPbCl ₃ 、CsPbI ₃ 、CsPbBr _(3-y) I _y (0＜y＜3)、CsPbBr _(3-y) Cl _y (0 < y < 3), but is not limited thereto.

As a preferred example of the perovskite compound having a three-dimensional structure, CH may be mentioned ₃ NH ₃ Pb _(1-a) Zn _a Br ₃ (0＜a≤0.7)、CH ₃ NH ₃ Pb _(1-a) Al _a Br _(3+δ) (0＜a≤0.7、0≤δ≤0.7)、CH ₃ NH ₃ Pb _(1-a) Co _a Br ₃ (0＜a≤0.7)、CH ₃ NH ₃ Pb _(1-a) Mn _a Br ₃ (0＜a≤0.7)、CH ₃ NH ₃ Pb _(1-a) Mg _a Br ₃ (0 < a.ltoreq.0.7), but is not limited thereto.

As a preferred example of the perovskite compound having a three-dimensional structure, csPb may be mentioned _(1-a) Zn _a Br ₃ (0＜a≤0.7)、CsPb _(1-a) Al _a Br _(3+δ) (0＜a≤0.7、0＜δ≤0.7)、CsPb _(1-a) Co _a Br ₃ (0＜a≤0.7)、CsPb _(1-a) Mn _a Br ₃ (0＜a≤0.7)、CsPb _(1-a) Mg _a Br ₃ (0 < a.ltoreq.0.7), but is not limited thereto.

As a preferred example of the perovskite compound having a three-dimensional structure, CH may be mentioned ₃ NH ₃ Pb _(1-a) Zn _a Br _(3-y) I _y (0＜a≤0.7、0＜y＜3)、CH ₃ NH ₃ Pb _(1-a) Al _a Br _(3+δ-y) I _y (0＜a≤0.7，0＜δ≤0.7，0＜y＜3)、CH ₃ NH ₃ Pb _(1-a) Co _a Br _(3-y) I _y (0＜a≤0.7、0＜y＜3)、CH ₃ NH ₃ Pb _(1-a) Mn _a Br _(3-y) I _y (0＜a≤0.7，0＜y＜3)、CH ₃ NH ₃ Pb _(1-a) Mg _a Br _(3-y) I _y (0＜a≤0.7、0＜y＜3)、CH ₃ NH ₃ Pb _(1-a) Zn _a Br _(3-y) Cl _y (0＜a≤0.7、0＜y＜3)、CH ₃ NH ₃ Pb _(1-a) Al _a Br _(3+δ-y) Cl _y (0＜a≤0.7、0＜δ≤0.7、0＜y＜3)、CH ₃ NH ₃ Pb _(1-a) Co _a Br _(3+δ-y) Cl _y (0＜a≤0.7、0＜δ≤0.7、0＜y＜3)、CH ₃ NH ₃ Pb _(1-a) Mn _a Br _(3-y) Cl _y (0＜a≤0.7、0＜y＜3)、CH ₃ NH ₃ Pb _(1-a) Mg _a Br _(3-y) Cl _y (0 < a.ltoreq.0.7, 0 < y < 3), but is not limited thereto.

Preferred examples of the perovskite compound having a three-dimensional structure include (H ₂ N＝CH-NH ₂ )Zn _a Br ₃ (0＜a≤0.7)、(H ₂ N＝CH-NH ₂ )Mg _a Br ₃ (0＜a≤0.7)、(H ₂ N＝CH-NH ₂ )Pb _(1-a) Zn _a Br _(3-y) I _y (0＜a≤0.7、0＜y＜3)、(H ₂ N＝CH-NH ₂ )Pb _(1-a) Zn _a Br _(3-y) Cl _y (0 < a.ltoreq.0.7, 0 < y < 3), but is not limited thereto.

Among the perovskite compounds having the above three-dimensional structure, csPbBr is more preferable ₃ 、CsPbBr _(3-y) I _y (0＜y＜3)、(H ₂ N＝CH-NH ₂ )PbBr ₃ Further preferably (H) ₂ N＝CH-NH ₂ )PbBr ₃ 。

(illustration of perovskite Compound of two-dimensional Structure)

Preferred examples of the perovskite compound having a two-dimensional structure include (C ₄ H ₉ NH ₃ ) ₂ PbBr ₄ 、(C ₄ H ₉ NH ₃ ) ₂ PbCl ₄ 、(C ₄ H ₉ NH ₃ ) ₂ PbI ₄ 、(C ₇ H ₁₅ NH ₃ ) ₂ PbBr ₄ 、(C ₇ H ₁₅ NH ₃ ) ₂ PbCl ₄ 、(C ₇ H ₁₅ NH ₃ ) ₂ PbI ₄ 、(C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Li _a Br _(4+δ) (0＜a≤0.7、-0.7≤δ＜0)、(C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Na _a Br _(4+δ) (0＜a≤0.7、-0.7≤δ＜0)、(C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Rb _a Br _(4+δ) (0 < a.ltoreq.0.7, -0.7.ltoreq.delta.ltoreq.0), but is not limited thereto.

Preferred examples of the perovskite compound having a two-dimensional structure include (C ₇ H ₁₅ NH ₃ ) ₂ Pb _(1-a) Na _a Br _(4+δ) (0＜a≤0.7、-0.7≤δ＜0)、(C ₇ H ₁₅ NH ₃ ) ₂ Pb _(1-a) Li _a Br _(4+δ) (0＜a≤0.7、-0.7≤δ＜0)、(C ₇ H ₁₅ NH ₃ ) ₂ Pb _(1-a) Rb _a Br _(4+δ) (0 < a.ltoreq.0.7, -0.7.ltoreq.delta.ltoreq.0), but is not limited thereto.

Preferred examples of the perovskite compound having a two-dimensional structure include (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Na _a Br _(4+δ-y) I _y (0＜a≤0.7、-0.7≤δ＜0、0＜y＜4)、(C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Li _a Br _(4+δ-y) I _y (0＜a≤0.7、-0.7≤δ＜0、0＜y＜4)、(C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Rb _a Br _(4+δ-y) I _y (0 < a.ltoreq.0.7, -0.7.ltoreq.delta.ltoreq.0, 0 < y < 4), but is not limited thereto.

Preferred examples of the perovskite compound having a two-dimensional structure include (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Na _a Br _(4+δ-y) Cl _y (0＜a≤0.7、-0.7≤δ＜0、0＜y＜4)、(C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Li _a Br _(4+δ-y) Cl _y (0＜a≤0.7、-0.7≤δ＜0、0＜y＜4)、(C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Rb _a Br _(4+δ-y) Cl _y (0 < a.ltoreq.0.7, -0.7.ltoreq.delta.ltoreq.0, 0 < y < 4), but is not limited thereto.

Preferred examples of the perovskite compound having a two-dimensional structure include (C ₄ H ₉ NH ₃ ) ₂ PbBr ₄ 、(C ₇ H ₁₅ NH ₃ ) ₂ PbBr ₄ But is not limited thereto.

Preferred examples of the perovskite compound having a two-dimensional structure include (C ₄ H ₉ NH ₃ ) ₂ PbBr _(4-y) Cl _y (0＜y＜4)、(C ₄ H ₉ NH ₃ ) ₂ PbBr _(4-y) I _y (0 < y < 4), but is not limited thereto.

Preferred examples of the perovskite compound having a two-dimensional structure include (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Zn _a Br ₄ (0＜a≤0.7)、(C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Mg _a Br ₄ (0＜a≤0.7)、(C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Co _a Br ₄ (0＜a≤0.7)、(C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Mn _a Br ₄ (0 < a.ltoreq.0.7), but is not limited thereto.

Preferred examples of the perovskite compound having a two-dimensional structure include (C ₇ H ₁₅ NH ₃ ) ₂ Pb _(1-a) Zn _a Br ₄ (0＜a≤0.7)、(C ₇ H ₁₅ NH ₃ ) ₂ Pb _(1-a) Mg _a Br ₄ (0＜a≤0.7)、(C ₇ H ₁₅ NH ₃ ) ₂ Pb _(1-a) Co _a Br ₄ (0＜a≤0.7)、(C ₇ H ₁₅ NH ₃ ) ₂ Pb _(1-a) Mn _a Br ₄ (0 < a.ltoreq.0.7), but is not limited thereto.

Preferred examples of the perovskite compound having a two-dimensional structure include (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Zn _a Br _(4-y) I _y (0＜a≤0.7、0＜y＜4)、(C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Mg _a Br _(4-y) I _y (0＜a≤0.7、0＜y＜4)、(C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Co _a Br _(4-y) I _y (0＜a≤0.7、0＜y＜4)、(C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Mn _a Br _(4-y) I _y (0 < a.ltoreq.0.7, 0 < y < 4), but is not limited thereto.

Preferred examples of the perovskite compound having a two-dimensional structure include (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Zn _a Br _(4-y) Cl _y (0＜a≤0.7、0＜y＜4)、(C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Mg _a Br _(4-y) Cl _y (0＜a≤0.7、0＜y＜4)、(C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Co _a Br _(4-y) Cl _y (0＜a≤0.7、0＜y＜4)、(C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Mn _a Br _(4-y) Cl _y (0 < a.ltoreq.0.7, 0 < y < 4), but is not limited thereto.

Particle size of perovskite Compound (1)

(1) The average particle diameter of the perovskite compound is preferably 13.5nm to 80.0 nm.

In one embodiment, the average particle diameter of the perovskite compound (1) is preferably 15.0nm or more, more preferably 17.0nm or more, and even more preferably 18.0nm or more, from the viewpoint that the perovskite compound (1) can be stably dispersed in the dispersion. In other embodiments, from the viewpoint of obtaining (1) a perovskite compound having high light emission intensity, the average particle diameter of (1) the perovskite compound is preferably 80.0nm or less, more preferably 25.0nm or less, and still more preferably 22.0nm or less.

In other embodiments, the perovskite compound has an average particle size of 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79nm or more.

In other embodiments, the perovskite compound has an average particle size of 85, 84, 83, 82, 81, 80, 79, 78, 77, 76, 75, 74, 73, 72, 71, 70, 69, 68, 67, 66, 65, 64, 63, 62, 61, 60, 59, 58, 57, 56, 55, 54, 53, 52, 51, 50, 49, 48, 47, 46, 45, 44, 43, 42, 41, 40, 39, 38, 37, 36, 35, 34, 33, 32, 31, 30, 29, 28, 27, 26, 25, 24, 23, 22, 21, 20, 19, 18, 17, 16, 15, 14, 13nm or less.

In the present specification, the average particle diameter of the (1) perovskite compound may be measured, for example, by a transmission electron microscope (hereinafter, also referred to as tem) or a scanning electron microscope (hereinafter, also referred to as sem). Specifically, the average particle diameter can be obtained by measuring the lengths of the longest sides of the particles of the randomly selected 30 or more (1) perovskite compounds in the form of cubes or rectangles, and calculating the arithmetic average of the measured values by TEM or SEM.

As a method for observing the perovskite compound (1) of the present embodiment, for example, a method for observing a dispersion composition containing the perovskite compound (1) using SEM, TEM, or the like is given. Further, by energy dispersive X-ray analysis (EDX) measurement using SEM or TEM, detailed analysis of element distribution can be performed. For the sake of high spatial resolution, a method of observation with TEM is preferable.

As a method of observing the perovskite compound (1) by TEM, there is a method of using a sample obtained by casting a dispersion composition containing the perovskite compound (1) on a grid with a support film dedicated to TEM and naturally drying the same.

As a method of analyzing the average particle diameter of the perovskite compound (1), a method of loading a TEM image into a computer and analyzing the same using image analysis software is exemplified.

First, the TEM image is loaded into a computer and binarized using image analysis software. A binarized image was obtained in which the perovskite compound of (1) was converted to black and the other was white. At this time, it was compared with an element distribution (mapping) chart obtained in the TEM-EDX measurement, and it was confirmed that the detected portion of the component derived from the perovskite compound of (1) had been converted to black. When a difference is found, the threshold value for performing binarization processing is adjusted. For the binarized image, the average particle diameter of the perovskite compound of (1) was measured using image analysis software. Image analysis software may appropriately select Image J, photoshop, and the like.

In another aspect of this embodiment, (1) the perovskite compound is a perovskite aggregate obtained by aggregating a plurality of compounds having the perovskite crystal structure. The perovskite aggregate is composed of one or more than two compounds with perovskite crystal structures. Thus, the perovskite aggregates are composed of one or more 1-valent cations, metal ions, or anions.

< composition 1 >

The composition 1 of the present embodiment contains the perovskite compound of the above (1) and at least one compound selected from the group consisting of the following (2-1), a modified product of the following (2-1), the following (2-2) and a modified product of the following (2-2).

(2-1) silazanes

In the present specification, at least one compound selected from the group consisting of the (2-1), the modified product of the (2-1), the (2-2) and the modified product of the (2-2) is sometimes collectively referred to as "(2) a surface protecting agent".

In one embodiment, the composition 1 of the present embodiment preferably contains the perovskite compound (1) and at least one compound selected from the group consisting of the (2-1) and the modified product of the (2-1).

The composition 1 of the present embodiment may further include at least one selected from the group consisting of the following (3), the following (4) and the following (5).

(3) Solvent(s)

(4) Polymerizable compound

(5) Polymer

< composition 2 >

The composition 2 of the present embodiment includes: the perovskite compound of the above (1), and at least one selected from the group consisting of the (3), the (4) and the (5).

In the following description, (3) a solvent, (4) a polymerizable compound, and (5) a polymer are sometimes collectively referred to as "dispersion medium". In the compositions 1 and 2 of the present embodiment, (1) the perovskite compound may be dispersed in these dispersion media.

In the present specification, "dispersed in" means (1) a state in which the perovskite compound is suspended in a dispersion medium or (1) a state in which the perovskite compound is suspended in a dispersion medium. (1) When the perovskite compound is dispersed in the dispersion medium, a part of the perovskite compound (1) may be precipitated.

The composition 1 and the composition 2 of the present embodiment may further comprise the following (6). The following (6) will be described specifically.

(6) Surface modifier

The composition 1 and the composition 2 of the present embodiment may have other components than the above (1) to (6). For example, the composition of the present embodiment may further comprise: a compound having an amorphous structure composed of elements constituting the perovskite compound of (1), a polymerization initiator.

Hereinafter, the above (2) to (6) contained in the composition of the present embodiment will be described.

(2) surface protective Agents

The composition 1 of the present embodiment may contain, as the (2) surface protecting agent for the perovskite compound (1), at least one compound selected from the group consisting of (2-1) silazanes, modified products of the (2-1), (2-2) silicon compounds having at least one group selected from the group consisting of amino groups, alkoxy groups and alkylthio groups, and modified products of the (2-2).

The composition 1 of the present embodiment can obtain effects such as an improvement in quantum yield and a reduction in the wavelength of emitted light by covering the surface of the perovskite compound of (1) with the surface protecting agent of (2).

(2-1) silazane

(2-1) silazane is a compound having Si-N-Si bond. The silazane may be any of linear, branched or cyclic.

The silazane may be a low molecular silazane or a high molecular silazane. In the present specification, the polymeric silazane may be referred to as polysilazane.

In the present specification, "low molecular weight" means that the number average molecular weight is less than 600.

In the present specification, "polymer" means a polymer having a number average molecular weight of 600 to 2000.

The term "number average molecular weight" as used herein refers to a polystyrene equivalent measured by Gel Permeation Chromatography (GPC).

(2-1-1. Low molecular silazanes)

The low-molecular silazane is preferably, for example, a disilazane represented by the following formula (B1).

[ chemical formula 2 ]

In the formula (B1), R ¹⁴ And R is ¹⁵ Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkylsilyl group having 1 to 20 carbon atoms.

R ¹⁴ And R is ¹⁵ May have a substituent such as an amino group. Multiple R' s ¹⁵ May be the same or different.

As the low molecular silazane represented by the formula (B1), examples thereof include 1, 3-divinyl-1, 3-tetramethyldisilazane 1, 3-diphenyl tetramethyl disilazane and 1, 3-hexamethyl disilazane, but is not limited thereto.

(2-1-2. Low molecular silazanes)

As the low molecular silazane, for example, a low molecular silazane represented by the following formula (B2) is also preferable.

[ chemical 3 ]

In the formula (B2), R ¹⁴ And R is ¹⁵ R is the same as R in the above formula (B1) ¹⁴ And R is ¹⁵ The same applies.

Multiple R' s ¹⁴ May be the same or different.

Multiple R' s ¹⁵ May be the same or different.

In the formula (B2), n ₁ And represents an integer of 1 to 20 inclusive. n is n ₁ The integer may be 1 to 10, or 1 or 2.

Examples of the low molecular silazane represented by the formula (B2) include octamethyl cyclotetrasilazane, 2,4, 6-hexamethylcyclotrisilazane and 2,4, 6-trimethyl-2, 4, 6-trivinylcyclotrisilazane, but are not limited thereto.

In one embodiment, the low molecular weight silazane is preferably octamethyl cyclotetrasilazane or 1, 3-diphenyl tetramethyldisilazane, and more preferably octamethyl cyclotetrasilazane.

(2-1-3. Polymer silazane)

The polymeric silazane is preferably, for example, polymeric silazane (polysilazane) represented by the following formula (B3).

Polysilazane is a high molecular compound having a Si-N-Si bond. The structural unit of polysilazane represented by the formula (B3) may be one or more.

[ chemical formula 4 ]

In the formula (B3), R ¹⁴ And R is ¹⁵ R is the same as R in the above formula (B1) ¹⁴ And R is ¹⁵ The same applies.

In formula (B3), the bonding site is represented. Bonding R at the bonding site of N atom at the end of molecular chain ¹⁴ 。

Bonding R at the bonding site of Si atom at the end of molecular chain ¹⁵ 。

Multiple R' s ¹⁴ May be the same or different.

Multiple R' s ¹⁵ May be the same or different.

m represents an integer of 2 to 10000 inclusive.

The polysilazane of the formula (B3) may be, for example, all R ¹⁴ And R is ¹⁵ Perhydro polysilazanes, all of which are hydrogen atoms.

The polysilazane represented by the formula (B3) may be, for example, at least one R ¹⁵ An organopolysiloxane that is a group other than a hydrogen atom. The perhydro polysilazane and the organopolysiloxane may be appropriately selected according to the application, or may be used by mixing them.

In one embodiment, the composition of the present embodiment preferably contains an organopolysiloxane represented by formula (B3) in order to improve dispersibility of (1) and to improve the effect of suppressing aggregation.

As the organopolysiloxane represented by the formula (B3), R may be used ¹⁴ And R is ¹⁵ At least one of them is an alkyl group having 1 to 20 carbon atoms,An organopolysiloxane of alkenyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, or alkylsilyl groups having 1 to 20 carbon atoms.

In one embodiment, among the organopolysiloxane, R represented by formula (B3) is preferred ¹⁴ And R is ¹⁵ At least one of which is a methyl group.

(2-1-4. Polymer silazane)

As the polymeric silazane, for example, polysilazane having a structure represented by the following formula (B4) is also preferable.

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

[ chemical 5 ]

In formula (B4), the bonding site is represented.

The bonding site of the formula (B4) may be bonded to the bonding site of the polysilazane of the formula (B3) or the bonding site of the structural unit of the polysilazane of the formula (B3).

In addition, when polysilazane contains a plurality of structures represented by the formula (B4) in a molecule, the bonding site of the structure represented by the formula (B4) may be directly bonded to the bonding site of the structure represented by another formula (B4).

R is bonded to a bonding site of polysilazane represented by the formula (B3), a bonding site of a structural unit of polysilazane represented by the formula (B3) and a bonding site of an N atom which is not bonded to any of bonding sites of other structures represented by the formula (B4) ¹⁴ 。

R is bonded to a Si atom bonding site which is not bonded to any of a bonding site of polysilazane represented by the formula (B3), a bonding site of a structural unit of polysilazane represented by the formula (B3) and a bonding site of a structure represented by the other formula (B4) ¹⁵ 。

In one embodiment, n ₂ And represents an integer of 1 to 10000 inclusive. n is n ₂ Can be 1 or moreThe integer of 10 or less may be 1 or 2.

In order to improve the dispersibility of (1) and to improve the effect of suppressing aggregation, the composition of the present embodiment preferably contains an organopolysiloxane having a structure represented by formula (B4).

As the organopolysiloxane having a structure represented by formula (B4), there may be mentioned at least one bonding site and R ¹⁴ Or R is ¹⁵ Bonding, the R ¹⁴ And R is ¹⁵ At least one of them is an organopolysiloxane containing an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkylsilyl group having 1 to 20 carbon atoms.

Of these, it is also preferable to include a structure represented by the formula (B4), at least one bonding site and R ¹⁴ Or R is ¹⁵ Bonding, the R ¹⁴ And R is ¹⁵ At least one of which is a methyl polysilazane.

The general polysilazane has, for example, a structure having a linear structure and a ring structure such as a 6-membered ring or an 8-membered ring, that is, a structure represented by the above formula (B3) or the above formula (B4). The molecular weight of a general polysilazane is about 600 to 2000 as a number average molecular weight (Mn) (in terms of polystyrene), and may be liquid or solid depending on the molecular weight.

The polysilazane may be commercially available products, and examples thereof include NN120-10, NN120-20, NAX-20, NN110, NAX, NAX110, NL120A, NL110A, NL150A, NP, NP140 (manufactured by AZ ELECTRONIC MATERIALS Co., ltd.), and AZNN-120-20, durazane (registered trademark) 1500Slow Cure, durazane1500 fast Cure, durazane 1800, durazane 1033 (manufactured by Merck Performance Materials Co., ltd.).

In one embodiment, the polysilazane is preferably AZNN-120-20, durazane1500 Slow Cure, durazane1500 Rapid Cure, and more preferably Durazane1500 Slow Cure.

Modified silazane of (2-1)

In the present specification, "modifying" means hydrolyzing a silicon compound having a Si-N bond, a Si-SR bond (R is a hydrogen atom OR an organic group), OR a Si-OR bond (R is a hydrogen atom OR an organic group) to produce a silicon compound having a Si-O-Si bond. Si-O-Si bonds can be formed by intermolecular condensation reactions or intramolecular condensation reactions.

The "modified body" in the present specification means a compound obtained by modifying a silicon compound having a Si-N bond, a Si-SR bond OR a Si-OR bond.

The modified product of (2-1) is preferably a modified product of disilazane represented by the formula (B1), a modified product of low-molecular silazane represented by the formula (B2), a modified product of polysilazane represented by the formula (B3), or a modified product of polysilazane having a structure represented by the formula (B4) in the molecule.

In one embodiment, the ratio of silicon atoms not bonded to nitrogen atoms in the modified low-molecular silazane represented by the formula (B2) is preferably 0.1 to 100% based on all silicon atoms contained in the modified low-molecular silazane represented by the formula (B2). In other embodiments, the proportion of silicon atoms not bonded to nitrogen atoms is more preferably 10 to 98%, and still more preferably 30 to 95%.

The "proportion of silicon atoms not bonded to nitrogen atoms" can be obtained as ((Si (mol)) - (N (mol) in Si-N bonds)))/Si (mol). Times.100 using the measurement values described later. In the case of the modification reaction, the "proportion of silicon atoms not bonded to nitrogen atoms" means "proportion of silicon atoms contained in siloxane bonds generated in the modification treatment".

In one embodiment, the modified polysilazane represented by the formula (B3) preferably has a proportion of silicon atoms not bonded to nitrogen atoms of 0.1 to 100% relative to all silicon atoms contained in the modified polysilazane represented by the formula (B3). In other embodiments, the proportion of silicon atoms not bonded to nitrogen atoms is more preferably 10 to 98%, and still more preferably 30 to 95%.

In one embodiment, the modified polysilazane having the structure represented by the formula (B4) preferably has a proportion of silicon atoms not bonded to nitrogen atoms of 0.1 to 99% relative to all silicon atoms contained in the modified polysilazane having the structure represented by the formula (B4). In another embodiment, the proportion of silicon atoms not bonded to nitrogen atoms is 10 to 97%, and more preferably 30 to 95%.

The number of Si atoms and the number of Si-N bonds in the modified product can be measured by X-ray photoelectron spectroscopy (XPS).

In one embodiment, the "proportion of silicon atoms not bonded to nitrogen atoms" of all silicon atoms, which is determined by the measurement value obtained by the above method, is preferably 0.1 to 99%, more preferably 10 to 99%, and even more preferably 30 to 95% with respect to the modified body.

(2-2) silicon compound having at least one group selected from the group consisting of amino group, alkoxy group and alkylthio group

The composition 1 of the present embodiment may contain (2-2) a silicon compound having at least one group selected from the group consisting of an amino group, an alkoxy group and an alkylthio group. Hereinafter, (2-2) a silicon compound having at least one group selected from the group consisting of an amino group, an alkoxy group and an alkylthio group is sometimes referred to collectively as "(2-2) a silicon compound".

As the (2-2) silicon compound, 3-aminopropyl triethoxysilane, 3-aminopropyl trimethoxysilane, dodecyl trimethoxysilane, trimethoxyphenyl silane, 1H, 2H-perfluorooctyl triethoxysilane, trimethoxy (1H, 2H-nonafluorohexyl) silane, 3-mercaptopropyl trimethoxysilane, 3-mercaptopropyl triethoxysilane are exemplified.

In one embodiment, among the silicon compounds, 3-aminopropyl triethoxysilane, 3-aminopropyl trimethoxysilane, trimethoxyphenylsilane, and more preferably trimethoxyphenylsilane are preferable from the viewpoint of durability of (1).

Modified body of silicon compound (2-2)

The modified product of the (2-2) silicon compound means a compound obtained by modifying the above-mentioned (2-2) silicon compound. The "modification" is the same as the description of the modified silazane of (2-1).

In the composition 1 of the present embodiment, only one of the above-mentioned (2) surface protecting agents may be used, or two or more kinds may be used in combination.

(6) surface modifier

The surface of the perovskite compound of (1) of this embodiment may be covered with the surface modifier layer. The surface modifier layer is located between (1) the perovskite compound and (2) the surface protecting agent.

The term "surface" of the surface modifier layer covering the perovskite compound of (1) means that the surface modifier layer is directly covered on the perovskite compound of (1), and includes a surface of other layer formed on the surface of the perovskite compound of (1) in direct contact with the surface of the perovskite compound of (1) and is covered without being in direct contact with the surface of the perovskite compound of (1).

< surface modifier layer >)

The surface modifier layer contains, as a forming material, at least one ion or compound selected from the group consisting of ammonium ions, amines, primary to tertiary ammonium cations, ammonium salts, carboxylic acids, carboxylate ions, and carboxylates.

Among them, the surface modifier layer preferably has at least one selected from the group consisting of amines and carboxylic acids as a forming material.

Hereinafter, the material for forming the surface modifier layer is sometimes referred to as "(6) surface modifier".

The surface modifier is a compound which has a function of covering the surface of the perovskite compound (1) and stably dispersing the perovskite compound (1) in the composition when the composition of the present embodiment is produced by a production method described later.

< ammonium ion, primary-tertiary ammonium cation, ammonium salt >

The ammonium ion and the primary to tertiary ammonium cations as the surface modifier (6) are represented by the following formula (A1). The ammonium salt as the surface modifier (6) is a salt containing an ion represented by the following formula (A1).

[ 6 ] A method for producing a polypeptide

In the ion represented by the formula (A1), R ¹ ～R ⁴ Represents a hydrogen atom or a 1-valent hydrocarbon group.

R ¹ ～R ⁴ The hydrocarbon group shown may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. Examples of the saturated hydrocarbon group include an alkyl group and a cycloalkyl group.

R ¹ ～R ⁴ The alkyl group may be linear or branched.

In one embodiment, R ¹ ～R ⁴ The number of carbon atoms of the alkyl group is usually 1 to 20, preferably 5 to 20, more preferably 8 to 20.

In one embodiment, the number of carbon atoms of the cycloalkyl group is usually 3 to 30, preferably 3 to 20, more preferably 3 to 11. The number of carbon atoms includes the number of carbon atoms of the substituent.

R ¹ ～R ⁴ The unsaturated hydrocarbon group of (2) may be linear or branched.

In one embodiment, R ¹ ～R ⁴ The number of carbon atoms of the unsaturated hydrocarbon group is usually 2 to 20, preferably 5 to 20, more preferably 8 to 20.

In one embodiment, R ¹ ～R ⁴ Each independently is preferably a hydrogen atom, an alkyl group or an unsaturated hydrocarbon group.

In one embodiment, the unsaturated hydrocarbon group is preferably an alkenyl group. In one embodiment, R ¹ ～R ⁴ Alkenyl groups having 8 to 20 carbon atoms are preferable independently of each other.

As R ¹ ～R ⁴ Specific examples of alkyl groups of (2) include R ⁶ ～R ⁹ Alkyl groups exemplified in (a).

As R ¹ ～R ⁴ Specific examples of cycloalkyl groups of (2) include R ⁶ ～R ⁹ Cycloalkyl groups as exemplified in (a).

As R ¹ ～R ⁴ Alkenyl groups of (2) may be exemplified as those in R ⁶ ～R ⁹ The position of the double bond is not limited, and the single bond (c—c) between any carbon atoms of the straight-chain or branched alkyl group exemplified in (a) is substituted with the double bond (c=c).

In one embodiment, R is ¹ ～R ⁴ Preferable examples of the alkenyl group of (2) include, for example, ethenyl, propenyl, 3-butenyl, 2-pentenyl, 2-hexenylRadical, 2-nonenyl, 2-dodecenyl, 9-octadecenyl, but not limited thereto.

When the ammonium cation represented by the formula (A1) forms a salt, the counter anion is not particularly limited. As the counter anion, a halide ion, a carboxylate ion, or the like is preferable. Examples of the halogen ion include bromide ion, chloride ion, iodide ion, and fluoride ion.

As ammonium salts having an ammonium cation and a counter anion represented by the formula (A1), n-octylammonium salt and oleylammonium salt are preferable.

< amine >)

Examples of the amine as the surface modifier include amines represented by the following formula (a 11).

[ chemical 7 ]

In the above formula (A11), R ¹ ～R ³ R is represented by the formula (A1) ¹ ～R ³ The same groups. Wherein R is ¹ ～R ³ At least one of which is a 1-valent hydrocarbon group.

The amine used as the surface modifier in one embodiment may be any of primary to tertiary amines, and is preferably a primary amine or a secondary amine, and more preferably a primary amine.

In one embodiment, the amine used as the surface modifier is preferably oleylamine.

< carboxylic acid, carboxylate ion, carboxylate salt >)

Carboxylate ions as surface modifiers are represented by the following formula (A2). The carboxylate as the surface modifier is a salt containing an ion represented by the following formula (A2).

R ⁵ -CO ₂ ^- ···(A2)

Examples of the carboxylic acid as the surface modifier include a carboxylic acid having a proton (H) bonded to the carboxylate ion represented by the above (A2) ⁺ ) But is not limited thereto.

In the ion represented by the formula (A2), R ⁵ Represents a monovalent hydrocarbon group. R is R ⁵ The hydrocarbon radicals shown may be saturated hydrocarbonsThe radical may also be an unsaturated hydrocarbon radical.

Examples of the saturated hydrocarbon group include, but are not limited to, an alkyl group and a cycloalkyl group.

R ⁵ The alkyl group may be linear or branched.

In one embodiment, R ⁵ The number of carbon atoms of the alkyl group is usually 1 to 20, preferably 5 to 20, more preferably 8 to 20.

The number of carbon atoms of the cycloalkyl group is usually 3 to 30, preferably 3 to 20, more preferably 3 to 11. The number of carbon atoms also includes the number of carbon atoms of the substituent.

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

In one embodiment, R ⁵ The number of carbon atoms of the unsaturated hydrocarbon group is usually 2 to 20, preferably 5 to 20, more preferably 8 to 20.

R ⁵ Preferably alkyl or unsaturated hydrocarbon groups. As the unsaturated hydrocarbon group, an alkenyl group is preferable.

As R ⁵ Specific examples of alkyl groups of (2) include R ⁶ ～R ⁹ Alkyl groups exemplified in (a).

As R ⁵ Specific examples of cycloalkyl groups of (2) include R ⁶ ～R ⁹ Cycloalkyl groups as exemplified in (a).

As R ⁵ Specific examples of alkenyl groups of (2) include R ¹ ～R ⁴ Alkenyl groups exemplified in (a).

In one embodiment, the carboxylate ion represented by formula (A2) is preferably an oleate anion.

When the carboxylate anion forms a salt, the counter cation is not particularly limited, but alkali metal cations, alkaline earth metal cations, ammonium cations, and the like are preferable.

As the carboxylic acid of the surface modifier, oleic acid is preferable.

Among the above-mentioned surface modifying agents, ammonium salts, ammonium ions, primary to tertiary ammonium cations, carboxylates, and carboxylate ions are preferable.

Of the ammonium salts and ammonium ions, oleylamine salts and oleylammonium ions are more preferable.

Among the carboxylate and carboxylate ions, oleate and oleate anions are more preferred.

The composition 1 and the composition 2 of the present embodiment may have only one kind of the above-mentioned (6) surface modifier, or two or more kinds may be used in combination.

Solvent < (3)

The solvent of the composition of the present embodiment is not particularly limited as long as it is a medium capable of dispersing the perovskite compound of (1) of the present embodiment. The solvent of the composition of the present embodiment preferably does not easily dissolve the perovskite compound (1) of the present embodiment.

In the present specification, "solvent" means a substance which is in a liquid state at 25 ℃ under 1 atmosphere. The solvent does not include a polymerizable compound described later.

The solvent may be any of the following (a) to (k), but is not limited thereto.

(a) Esters of

(b) Ketone compounds

(c) Ethers

(d) Alcohols

(e) Glycol ethers

(f) Organic solvent having amide group

(g) Organic solvent having nitrile group

(h) Organic solvent having carbonate group

(i) Halogenated hydrocarbons

(j) Hydrocarbons

(k) Dimethyl sulfoxide

Examples of the ester (a) include, but are not limited to, methyl formate, ethyl formate, propyl formate, pentyl formate, methyl acetate, ethyl acetate, and amyl acetate.

Examples of the ketone (b) include, but are not limited to, gamma-butyrolactone, N-methyl-2-pyrrolidone, acetone, diisobutylketone, cyclopentanone, cyclohexanone, and methylcyclohexanone.

Examples of the ether (c) include diethyl ether, methyl tert-butyl ether, diisopropyl ether, dimethoxymethane, dimethoxyethane, 1, 4-dioxane, 1, 3-dioxolane, 4-methyldioxolane, tetrahydrofuran, methyltetrahydrofuran, anisole, phenetole, and the like, but are not limited thereto.

Examples of the alcohol (d) include, but are not limited to, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, t-butanol, 1-pentanol, 2-methyl-2-butanol, methoxypropanol, diacetone alcohol, cyclohexanol, 2-fluoroethanol, 2-trifluoroethanol, 2, 3-tetrafluoro-1-propanol, and the like.

Examples of the glycol ether (e) include, but are not limited to, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, triethylene glycol dimethyl ether, and the like.

Examples of the (f) organic solvent having an amide group include, but are not limited to, N-dimethylformamide, acetamide, and N, N-dimethylacetamide.

Examples of the organic solvent having a nitrile group (g) include acetonitrile, isobutyronitrile, propionitrile, methoxyacetonitrile, and the like, but are not limited thereto.

Examples of the organic solvent (h) having a carbonate group include, but are not limited to, ethylene carbonate and propylene carbonate.

Examples of the halogenated hydrocarbon (i) include methylene chloride and chloroform, but are not limited thereto.

Examples of the hydrocarbon (j) include, but are not limited to, n-pentane, cyclohexane, n-hexane, 1-octadecene, benzene, toluene, xylene, and the like.

In one embodiment, among these solvents, (a) esters, (b) ketones, (c) ethers, (g) organic solvents having nitrile groups, (h) organic solvents having carbonate groups, (i) halogenated hydrocarbons, and (j) hydrocarbons are considered to have low polarity, and it is preferable to dissolve the perovskite compound (1) of the present embodiment.

Further, as the solvent used in the composition of the present embodiment, (i) a halogenated hydrocarbon and (j) a hydrocarbon are more preferable.

In the composition 1 and the composition 2 of the present embodiment, only one of the above solvents may be used, or two or more of them may be used in combination.

(4) polymerizable Compound

The polymerizable compound of the composition of the present embodiment is preferably a substance which is difficult to dissolve the perovskite compound (1) of the present embodiment at the temperature at which the composition of the present embodiment is produced.

In the present specification, the "polymerizable compound" refers to a monomer compound (monomer) having a polymerizable group. Examples of the polymerizable compound include monomers which are in a liquid state at 25℃under 1 atm.

For example, the polymerizable compound is not particularly limited when the production is carried out at normal temperature and normal pressure. Examples of the polymerizable compound include known polymerizable compounds such as styrene, acrylate, methacrylate, and acrylonitrile. Among them, any one or both of acrylic acid ester and methacrylic acid ester as acrylic resin monomers are preferable as the polymerizable compound.

In the composition 1 and the composition 2 of the present embodiment, only one kind of polymerizable compound may be used, or two or more kinds may be used in combination.

In the composition of the present embodiment, the ratio of the total amount of the acrylic acid ester and the methacrylic acid ester to the total amount of all the polymerizable compounds (4) may be 10mol% or more. The proportion may be 30mol% or more, or may be 50mol% or more, or may be 80mol% or more, or may be 100mol% or more.

(5) Polymer

The polymer contained in the composition of the present embodiment is preferably a polymer having low solubility of the perovskite compound of (1) of the present embodiment at the temperature at which the composition of the present embodiment is produced.

For example, in the case of production at normal temperature and normal pressure, the polymer is not particularly limited, and examples thereof include known polymers such as polystyrene, acrylic resin and epoxy resin. Among them, an acrylic resin is preferable as the polymer. The acrylic resin may contain either or both of structural units derived from an acrylic acid ester and structural units derived from a methacrylic acid ester.

In the composition of the present embodiment, the ratio of the total amount of the structural units derived from the acrylic acid ester and the structural units derived from the methacrylic acid ester may be 10mol% or more with respect to all the structural units contained in the polymer (5). The proportion may be 30mol% or more, 50mol% or more, 80mol% or more, or 100mol% or more.

(5) The weight average molecular weight of the polymer is preferably 100 to 1200000, more preferably 1000 to 800000, and even more preferably 5000 to 150000.

The term "weight average molecular weight" as used herein refers to a polystyrene equivalent measured by Gel Permeation Chromatography (GPC).

In the composition 1 and the composition 2 of the present embodiment, only one of the above-mentioned (5) polymers may be used, or two or more of them may be used in combination.

< content of each component in composition >

In the compositions 1 and 2 of the present embodiment, the content ratio of the perovskite compound (1) relative to the total mass of the composition is not particularly limited.

In one embodiment, the content is preferably 90 mass% or less, more preferably 40 mass% or less, further preferably 10 mass% or less, and particularly preferably 3 mass% or less, from the viewpoint of preventing concentration quenching.

In another embodiment, the content is preferably 0.0002 mass% or more, more preferably 0.002 mass% or more, and still more preferably 0.01 mass% or more, from the viewpoint of obtaining a good quantum yield.

The upper limit and the lower limit may be arbitrarily combined.

The content of the perovskite compound (1) is usually 0.0002 to 90% by mass based on the total mass of the composition.

In one embodiment, the content of the perovskite compound (1) is preferably 0.001 to 40% by mass, more preferably 0.002 to 10% by mass, and even more preferably 0.01 to 3% by mass, based on the total mass of the composition.

In one embodiment, the content ratio of the perovskite compound (1) is 0.0002, 0.0005, 0.001, 0.002, 0.005, 0.01, 0.05, 0.1, 0.5, 1, 10, 20, 30, 40, 50, 60, 70, 80 mass% or more.

In other embodiments, the content of the perovskite compound (1) is 90, 80, 70, 60, 50, 40, 30, 20, 10, 1, 0.5, 0.1, 0.05, 0.01, 0.005, 0.002, 0.001, 0.0005 mass% or less.

The composition having the content ratio of the perovskite compound (1) in the above range relative to the total mass of the composition is preferable in that the perovskite compound (1) is less likely to aggregate and excellent light-emitting properties can be exhibited.

In the composition 1 of the present embodiment, the content ratio of the surface protecting agent (2) relative to the total mass of the composition is not particularly limited.

In one embodiment, the content is preferably 30 mass% or less, more preferably 10 mass% or less, and still more preferably 7.5 mass% or less, from the viewpoint of improving the dispersibility of the perovskite compound (1) and the viewpoint of improving the durability.

In one embodiment, the content is preferably 0.001 mass% or more, more preferably 0.01 mass% or more, and even more preferably 0.1 mass% or more, from the viewpoint of improving durability.

In another embodiment, the content is 0.001, 0.005, 0.01, 0.05, 0.1, 0.5, 1, 5, 7.5, 10, 15, 20, 25 mass% or more. In another embodiment, the content ratio is 30, 25, 20, 15, 10, 7.5, 5, 1, 0.5, 0.1, or 0.05 mass% or less.

The upper limit and the lower limit may be arbitrarily combined.

In one embodiment, the content of the surface protecting agent (2) is usually 0.001 to 30% by mass based on the total mass of the composition.

In one embodiment, the content of the surface protecting agent (2) is preferably 0.001 to 30% by mass, more preferably 0.001 to 10% by mass, and even more preferably 0.1 to 7.5% by mass, based on the total mass of the composition.

In another embodiment, the content ratio of the surface protective agent (2) is 0.001, 0.01, 0.05, 0.1, 0.5, 1, 5, 7.5, 10, 15, 20, 25 mass% or more. In another embodiment, the content ratio of the surface protective agent (2) is 30, 25, 20, 15, 10, 7.5, 5, 1, 0.5, 0.1, 0.05 mass% or less.

In the compositions 1 and 2 of the present embodiment, the content ratio of the dispersion medium relative to the total mass of the composition is not particularly limited.

In one embodiment, the content ratio is preferably 99.99 mass% or less, more preferably 99.9 mass% or less, and still more preferably 99 mass% or less, from the viewpoint of improving the dispersibility of the perovskite compound (1) and the viewpoint of improving the durability.

In one embodiment, the content is preferably 0.1 mass% or more, more preferably 1 mass% or more, further preferably 10 mass% or more, further preferably 50 mass% or more, further preferably 80 mass% or more, and most preferably 90 mass% or more, from the viewpoint of improving durability.

The upper limit and the lower limit may be arbitrarily combined.

In one embodiment, the content of the dispersion medium is usually 0.1 to 99.99 mass% based on the total mass of the composition.

In one embodiment, the content of the dispersion medium is preferably 1 to 99% by mass, more preferably 10 to 99% by mass, still more preferably 20 to 99% by mass, particularly preferably 50 to 99% by mass, and most preferably 90 to 99% by mass, based on the total mass of the composition.

In another embodiment, the content ratio of the dispersion medium is 1, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, 95 mass% or more. In another embodiment, the content of the dispersion medium is 99, 95, 90, 80, 70, 60, 50, 40, 30, 20, 10, or 5 mass% or less.

In one embodiment, the total content of the perovskite compound (1) and the surface protecting agent (2) and the dispersion medium in the composition may be 90 mass% or more, 95 mass% or more, 99 mass% or more, or 100 mass% or more, based on the total mass of the composition.

In the compositions 1 and 2 of the present embodiment, the content ratio of the surface modifier (6) relative to the total mass of the composition is not particularly limited.

In one embodiment, the content is preferably 30 mass% or less, more preferably 1 mass% or less, and still more preferably 0.1 mass% or less, from the viewpoint of improving durability.

In one embodiment, the content is preferably 0.0001 mass% or more, more preferably 0.001 mass% or more, and even more preferably 0.01 mass% or more, from the viewpoint of improving thermal durability.

In another embodiment, the content ratio is 0.001, 0.005, 0.01, 0.05, 0.1, 0.5, 1, 5, 10, 15, 20, 25 mass% or more. In another embodiment, the content ratio is 30, 25, 20, 15, 10, 5, 1, 0.5, 0.1, 0.05, 0.01, 0.005% by mass or less.

The upper limit and the lower limit may be arbitrarily combined.

In one embodiment, the content of the surface modifier (6) is usually 0.0001 to 30% by mass based on the total mass of the composition.

In one embodiment, the content of the surface modifier (6) is preferably 0.001 to 1% by mass, more preferably 0.01 to 0.1% by mass, based on the total mass of the composition.

In another embodiment, the content of the surface modifier (6) is 0.0001, 0.0005, 0.001, 0.005, 0.01, 0.05, 0.1, 0.5, 1, 5, 10, 15, 20, 25 mass% or more. In another embodiment, the content ratio of the surface modifier (6) is 30, 25, 20, 15, 10, 5, 1, 0.5, 0.1, 0.05, 0.01, 0.005% by mass or less.

The composition having the content ratio of the surface modifier (6) in the above range relative to the total mass of the composition is preferable from the viewpoint of excellent thermal durability.

In one embodiment, the total content of the impurity, the compound having an amorphous structure composed of the element constituting the perovskite compound (1), and the polymerization initiator in the composition of the present embodiment is preferably 10 mass% or less, more preferably 5 mass% or less, and still more preferably 1 mass% or less, based on the total mass of the composition.

< mixing ratio of ingredients >

In the compositions 1 and 2 of the present embodiment, the mass ratio of the perovskite compound (1) to the dispersion medium [ (1) perovskite compound/dispersion medium ] may be 0.00001 to 10, may be 0.0001 to 5, or may be 0.0005 to 3.

(1) The composition having the mixing ratio of the perovskite compound and the dispersion medium in the above range is preferable in that the perovskite compound is less likely to agglomerate (1) and the light emission is excellent.

In the composition 1 of the present embodiment, the mixing ratio of the (1) perovskite compound and the (2) surface protecting agent can be appropriately determined according to the types of the (1) and (2), and the like.

In the composition 1 of the present embodiment, the molar ratio [ Si/B ] of the Si element of the (2) surface protecting agent to the metal ion as the B component of the (1) perovskite compound may be 0.001 to 200 or 0.01 to 50.

In the composition 1 of the present embodiment, when the (2) surface protecting agent is a modified silazane represented by the formula (B1) or (B2), the molar ratio [ Si/B ] of Si of the modified silazane to the metal ion as the B component of the perovskite compound (1) may be 0.001 to 100, or 0.001 to 50, or 1 to 20.

In the composition 1 of the present embodiment, when the (2) surface protecting agent is polysilazane having a structural unit represented by the formula (B3), the molar ratio [ Si/B ] of the Si element of the modified silazane (2-1) to the metal ion as the B component of the perovskite compound (1) may be 0.001 to 100, 0.01 to 100, 0.1 to 100, 1 to 50, or 1 to 20.

(1) The composition having the mixing ratio of the perovskite compound and the (2) surface protecting agent within the above range is preferable from the viewpoint of particularly preferably exhibiting the effect of the (2) surface protecting agent on improving the durability against water vapor.

(2) The molar ratio [ Si/B ] of Si element of the surface protecting agent to metal ion as the B component of the perovskite compound can be determined by the following method.

The molar number (B) of metal ions as the B component of the perovskite compound is calculated by inductively coupled plasma mass spectrometry (ICP-MS), and then converted into moles. The molar number (Si) of the Si element of the (2) surface protective agent is obtained by molar conversion based on the mass of the (2) surface protective agent used.

The ratio of the number of moles of Si (Si) of the surface protecting agent (2) to the number of moles of metal ions (B) of the component B of the perovskite compound is [ Si/B ].

In one embodiment, the composition of the present embodiment preferably has a mass of 1.1 parts by mass or more, more preferably 1.5 parts by mass or more, and even more preferably 1.8 parts by mass or more, relative to the mass of (1) the perovskite compound, in order to sufficiently improve the quantum yield. In another embodiment, the mass of the surface protecting agent (2) is preferably 10 parts by mass or less, more preferably 4.9 parts by mass or less, and still more preferably 2.5 parts by mass or less, relative to the mass of the perovskite compound (1).

The upper limit and the lower limit may be arbitrarily combined.

According to the method for producing a semiconductor compound of the present embodiment, the perovskite compound of (1) of the present embodiment and the semiconductor compound containing the metal element M having a half width of a peak of the crystal face miller index (001) of 0.10 or more and less than 0.60 in the X-ray diffraction pattern can be produced.

Method for producing semiconductor compound

The method for producing a semiconductor compound according to the present embodiment includes: a step of mixing a raw material containing either or both of a simple substance of a metal element M and a compound containing the metal element M with water, and a step of reacting the raw material in the presence of the water. In addition, the mass W of the water _W W relative to the mass of the metal element M contained in the raw material _M Ratio (W) _W /W _M ) 0.05 to 100.

In the step of crystallizing the semiconductor compound by reacting a raw material containing either or both of the simple substance of the metal element M and the compound containing the metal element M, if water is present, a part of crystals of the semiconductor compound formed are dissolved, and then the semiconductor compound is recrystallized, thereby improving the crystallinity of the semiconductor compound.

< Metal element M >)

The metal element M contained in the method for producing a semiconductor compound according to the present embodiment includes examples of metal elements of columns 2 to 14 of the periodic table. The metal elements of columns 2 to 14 of the periodic table are not particularly limited, and examples thereof include Mg, ca, sr, ba, cu, zn, cd, hg, al, ga, in, sn, pb.

The semiconductor compound of the present embodiment may contain a nonmetallic element of columns 13 to 17 of the periodic table in addition to the metal element M. The nonmetallic elements of columns 13 to 17 of the periodic table are not particularly limited, and examples thereof include B, C, N, P, as, sb, se, te, F and Cl, br, I, S.

Examples of the semiconductor compound produced by the production method of the present embodiment include the perovskite compound (1) of the present embodiment and the semiconductor compounds (i) to (vii) described below.

(i) Semiconductor compounds comprising group II-VI compounds

(ii) Semiconductor compounds comprising group II-V compounds

(iii) Semiconductor compounds comprising group III-V compounds

(iv) Semiconductor compounds comprising group III-IV compounds

(v) Semiconductor compounds comprising group III-VI compounds

(vi) Semiconductor compounds comprising group IV-VI compounds

(vii) Semiconductor compounds comprising transition metal-p-region compounds

(i) semiconductor Compounds comprising group II-VI Compounds

Examples of the semiconductor compound containing a group II to group VI compound include, but are not limited to, a semiconductor compound containing a group 2 element and a group 16 element of the periodic table, and a semiconductor compound containing a group 12 element and a group 16 element of the periodic table.

In the present specification, the term "periodic table" means a long-period periodic table.

In the following description, a semiconductor compound including a compound containing a group 2 element and a group 16 element may be referred to as "semiconductor compound (i-1)", and a semiconductor compound including a compound containing a group 12 element and a group 16 element may be referred to as "semiconductor compound (i-2)".

In one embodiment, the binary semiconductor compound among the semiconductor compounds (i-1) is exemplified by MgS, mgSe, mgTe, caS, caSe, caTe, srS, srSe, srTe, baS, baSe and BaTe, but is not limited thereto.

In one embodiment, the semiconductor compound (i-1) may be

(i-1-1) ternary semiconductor compound containing 1 kind of group 2 element and 2 kinds of group 16 element

(i-1-2) ternary semiconductor compound containing 2 kinds of group 2 elements and 1 kind of group 16 elements

(i-1-3) a quaternary semiconductor compound containing 2 kinds of group 2 elements and 2 kinds of group 16 elements.

In one embodiment, the binary semiconductor compound among the semiconductor compounds (i-2) is exemplified by ZnS, znSe, znTe, cdS, cdSe, cdTe, hgS, hgSe and HgTe, but is not limited thereto.

In one embodiment, the semiconductor compound (i-2) may be

(i-2-1) ternary semiconductor compound containing 1 kind of group 12 element and 2 kinds of group 16 element

(i-2-2) ternary semiconductor compound containing 2 kinds of group 12 elements and 1 kind of group 16 elements

(i-2-3) a quaternary semiconductor compound containing 2 kinds of group 12 elements and 2 kinds of group 16 elements.

The group II-VI semiconductor compound may contain an element other than the group 2 element, the group 12 element, and the group 16 element as a doping element.

(II) a semiconductor compound comprising a group II-V compound

The group II-V semiconductor compound contains a group 12 element and a group 15 element.

Among the group II-group V semiconductor compounds, examples of binary semiconductor compounds include Zn ₃ P ₂ 、Zn ₃ As ₂ 、Cd ₃ P ₂ 、Cd ₃ As ₂ 、Cd ₃ N ₂ Or Zn ₃ N ₂ But is not limited thereto.

In one embodiment, the group II-V semiconductor compound may be

(ii-1) ternary semiconductor compound containing 1 kind of group 12 element and 2 kinds of group 15 element

(ii-2) ternary semiconductor compound containing 2 kinds of group 12 elements and 1 kind of group 15 elements

(ii-3) a quaternary semiconductor compound containing 2 kinds of group 12 elements and 2 kinds of group 15 elements.

The group II-V semiconductor compound may contain an element other than the group 12 element and the group 15 element as a doping element.

(III) semiconductor Compounds comprising group III-V Compounds

The group III-V semiconductor compound contains a group 13 element and a group 15 element.

Among the group III-V semiconductor compounds, examples of binary semiconductor compounds include AlP, alAs, alSb, gaN, gaP, gaAs, gaSb, inN, inP, inAs, inSb and AlN, but are not limited thereto.

In one embodiment, the group III-V semiconductor compound may be

(iii-1) ternary semiconductor compound containing 1 kind of group 13 element and 2 kinds of group 15 element

(iii-2) ternary semiconductor compound containing 2 kinds of group 13 elements and 1 kind of group 15 elements

(iii-3) a quaternary semiconductor compound containing 2 kinds of group 13 elements and 2 kinds of group 15 elements.

The group III-V semiconductor compound may contain an element other than the group 13 element and the group 15 element as a doping element.

(IV) semiconductor Compounds comprising group III-IV Compounds

The group III-IV semiconductor compound contains a group 13 element and a group 14 element.

Among the group III-group IV semiconductor compounds, examples of binary semiconductor compounds include Al ₄ C ₃ 、Ga ₄ C ₃ 。

Further, as the group III-IV semiconductor compound, there may be mentioned

(iv-1) ternary semiconductor compound containing 1 kind of group 13 element and 2 kinds of group 14 element

(iv-2) ternary semiconductor compound containing 2 kinds of group 13 elements and 1 kind of group 14 elements

(iv-3) a quaternary semiconductor compound containing 2 kinds of group 13 elements and 2 kinds of group 14 elements.

The group III-IV semiconductor compound may contain an element other than the group 13 element and the group 14 element as a doping element.

(v) semiconductor Compounds comprising group III-VI Compounds

The group III-VI semiconductor compound includes a column 13 element and a column 16 element.

Among the group III-VI semiconductor compounds, examples of binary semiconductor compounds include Al ₂ S ₃ 、Al ₂ Se ₃ 、Al ₂ Te ₃ 、Ga ₂ S ₃ 、Ga ₂ Se ₃ 、Ga ₂ Te ₃ 、GaTe、In ₂ S ₃ 、In ₂ Se ₃ 、In ₂ Te ₃ Or inee, but is not limited thereto.

In one embodiment, the group III-VI semiconductor compound,

(v-1) ternary semiconductor compound containing 1 kind of group 13 element and 2 kinds of group 16 element

(v-2) ternary semiconductor compound containing 2 kinds of group 13 elements and 1 kind of group 16 elements

(v-3) a quaternary semiconductor compound containing 2 kinds of group 13 elements and 2 kinds of group 16 elements.

The group III-VI semiconductor compound may contain an element other than the group 13 element and the group 16 element as a doping element.

(VI) semiconductor Compounds comprising group IV-VI Compounds

The group IV-VI semiconductor compound includes a column 14 element and a column 16 element.

Among the group IV-VI semiconductor compounds, examples of binary semiconductor compounds include PbS, pbSe, pbTe, snS, snSe and SnTe, but are not limited thereto.

In one embodiment, the group IV-VI semiconductor compound may be

(vi-1) ternary semiconductor compound containing 1 kind of group 14 element and 2 kinds of group 16 element

(vi-2) ternary semiconductor compound containing 2 kinds of group 14 elements and 1 kind of group 16 elements

(vi-3) a quaternary semiconductor compound containing 2 kinds of group 14 elements and 2 kinds of group 16 elements.

The group IV-VI semiconductor compound may contain an element other than the group 14 element and the group 16 element as a doping element.

(vii) semiconductor Compounds comprising transition Metal-p region Compounds

The transition metal-p-region semiconductor compound contains a transition metal element and a p-region element. "p-region element" means an element belonging to the groups 13 to 18 of the periodic table.

Among the transition metal-p region semiconductor compounds, binary semiconductor compounds include, for example, niS and CrS, but are not limited thereto.

In one embodiment, the transition metal-p region semiconductor compound may be

(vii-1) ternary semiconductor compound containing 1 transition metal element and 2 p-region elements

(vii-2) ternary semiconductor compound containing 2 transition metal elements and 1 p-region element

(vii-3) a quaternary semiconductor compound containing 2 transition metal elements and 2 p-region elements.

The transition metal-p-region semiconductor compound may contain a transition metal element and an element other than the p-region element as doping elements.

Specific examples of the ternary semiconductor compound and quaternary semiconductor compound include ZnCdS, cdSeS, cdSeTe, cdSTe, znSeS, znSeTe, znSTe, hgSeS, hgSeTe, hgSTe, cdZnS, cdZnSe, cdZnTe, cdHgS, cdHgSe, cdHgTe, hgZnS, hgZnSe, hgZnTe, znCdSSe, cdZnSeS, cdZnSeTe, cdZnSTe, cdHgSeS, cdHgSeTe, cdHgSTe, hgZnSeS, hgZnSeTe, hgZnSTe, gaNP, gaNAs, gaPAs, alNP, alNAs, alPAs, inNP, inNAs, inPAs, gaAlNP, gaAlNAs, gaAlPAs, gaInNP, gaInNAs, gaInPAs, inAlNP, inAlNAs, cuInS ₂ Or InAlPAs, etc., but is not limited thereto.

In one embodiment, the semiconductor compound according to the present embodiment is preferably (1) a perovskite compound according to the present embodiment, a semiconductor compound containing a group 12 element Cd, or a semiconductor compound containing a group 13 element In. In other embodiments, as the compound of the present embodiment, (1) a perovskite compound, a semiconductor compound containing Cd and Se, and a semiconductor compound containing In and P are more preferable.

In one embodiment, the semiconductor compound containing Cd and Se is preferably any one of a binary semiconductor compound, a ternary semiconductor compound, and a quaternary semiconductor compound. Among other modes, a binary semiconductor compound CdSe is particularly preferable among semiconductor compounds containing Cd and Se.

In one embodiment, the semiconductor compound containing In and P is preferably any one of a binary semiconductor compound, a ternary semiconductor compound, and a quaternary semiconductor compound. Among other modes, a binary semiconductor compound InP is particularly preferable among semiconductor compounds containing In and P.

Particle size of semiconductor Compound produced by the method for producing a semiconductor Compound of the present embodiment

The preferred average particle diameter of the semiconductor compound produced by the method for producing a semiconductor compound according to the present embodiment is the same as the average particle diameter of the perovskite compound (1) described above.

In the present specification, the average particle diameter of the semiconductor compound produced by the method for producing a semiconductor compound according to the present embodiment can be measured by the same method as the measurement of the average particle diameter of the perovskite compound (1) described above.

In the production of the semiconductor compound of the present embodiment, the following can be used: a raw material containing any one or both of a simple substance of the metal element M and a compound containing the metal element M (hereinafter, a raw material containing any one or both of a simple substance of the metal element M and a compound containing the metal element M is also referred to as "raw material containing the metal element M"). When the semiconductor compound contains a nonmetallic element, a compound further containing a nonmetallic element is preferably used as the raw material (hereinafter, the compound containing a nonmetallic element is also referred to as "raw material compound containing a nonmetallic element").

< simple substance of Metal element M >)

The simple substance of the metal element M is not particularly limited, and examples thereof include the simple substance of the metal element M described above.

< Compound containing Metal element M >

The compound containing the metal element M is not particularly limited, and examples thereof include oxides, acetates, organometallic compounds, halides, nitrates, and the like containing the metal element M.

In the production of the semiconductor compound according to the present embodiment, only one kind of the simple substance of the metal element M may be used, or two or more kinds may be used in combination.

In the production of the semiconductor compound according to the present embodiment, the compound containing the metal element M may be used alone or in combination of two or more.

< Compound containing nonmetallic element >

The raw material compound containing a nonmetallic element is not particularly limited, and a compound containing a nonmetallic element contained in a semiconductor compound can be used. In this embodiment, a compound containing a nonmetallic element of columns 13 to 17 of the periodic table can be used without limitation.

In the production of the semiconductor compound according to the present embodiment, only one kind of the raw material compound containing the nonmetallic element may be used, or two or more kinds may be used in combination.

((i) to (vii) method for producing semiconductor Compound)

(i) The semiconductor compounds (vii) can be produced by a method in which a raw material containing the metal element M constituting the semiconductor compound and a fat-soluble solvent are mixed to form a mixed solution, and the mixed solution is heated. In addition, it is preferable to add a compound containing a nonmetallic element constituting the semiconductor compound to the mixed solution as necessary.

Examples of the fat-soluble solvent include a nitrogen-containing compound having a hydrocarbon group having 4 to 20 carbon atoms, an oxygen-containing compound having a hydrocarbon group having 4 to 20 carbon atoms, and the like.

Examples of the hydrocarbon group having 4 to 20 carbon atoms include a saturated aliphatic hydrocarbon group, an unsaturated aliphatic hydrocarbon group, an alicyclic hydrocarbon group and an aromatic hydrocarbon group.

Examples of the saturated aliphatic hydrocarbon group having 4 to 20 carbon atoms include n-butyl, isobutyl, n-pentyl, octyl, decyl, dodecyl, hexadecyl, and octadecyl.

Examples of the unsaturated aliphatic hydrocarbon group having 4 to 20 carbon atoms include oleyl groups.

Examples of the alicyclic hydrocarbon group having 4 to 20 carbon atoms include cyclopentyl and cyclohexyl.

Examples of the aromatic hydrocarbon group having 4 to 20 carbon atoms include phenyl, benzyl, naphthyl, and naphthylmethyl.

The hydrocarbon group having 4 to 20 carbon atoms is preferably a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group.

Examples of the nitrogen-containing compound include amines and amides.

Examples of the oxygen-containing compound include fatty acids.

Among such fat-soluble solvents, nitrogen-containing compounds having a hydrocarbon group having 4 to 20 carbon atoms are preferable. Examples of the nitrogen-containing compound include alkylamines such as n-butylamine, isobutylamine, n-pentylamine, n-hexylamine, octylamine, decylamine, dodecylamine, hexadecylamine, and octadecylamine, and enamines such as oleylamine.

Such a fat-soluble solvent can be bonded to the surface of the semiconductor compound produced by synthesis. Examples of the bond when the fat-soluble solvent is bonded to the surface of the semiconductor compound include chemical bonds such as covalent bonds, ionic bonds, coordinate bonds, hydrogen bonds, and van der Waals bonds.

The heating temperature of the mixed solution may be appropriately set according to the kind of the raw material (monomer or compound) used. The temperature of the mixture is usually from room temperature to 300 ℃. For example, it is preferably 130 to 300℃and more preferably 240 to 300 ℃. When the heating temperature is not less than the above lower limit, the crystal structure is easily unified, which is preferable. When the heating temperature is not higher than the upper limit, the crystal structure of the semiconductor compound to be produced is not likely to collapse, and the target product is likely to be obtained, which is preferable.

In one embodiment, the heating temperature is 0, 5, 10, 50, 75, 100, 130, 150, 175, 200, or 250 ℃ or higher. In other embodiments, the heating temperature is 300, 250, 200, 175, 150, 130, 100, 75, 50, 10, or 5 ℃ or less.

The heating time of the mixed solution can be appropriately set according to the kind of the raw material (monomer or compound) to be used and the heating temperature. The heating time of the mixed solution is, for example, preferably several seconds to several hours, more preferably 1 to 60 minutes.

In the above method for producing a semiconductor compound, a precipitate containing the semiconductor compound as a target can be obtained by cooling the heated mixed solution. The precipitate is separated and appropriately washed to obtain a semiconductor compound as a target.

To the supernatant obtained by separating the precipitate, a solvent in which the synthesized semiconductor compound is insoluble or poorly soluble may be added, so that the solubility of the semiconductor compound in the supernatant is reduced to produce a precipitate, and the semiconductor compound contained in the supernatant may be recovered. Examples of the "solvent in which the semiconductor compound is insoluble or poorly soluble" include methanol, ethanol, acetone, acetonitrile, and the like.

In the above method for producing a semiconductor compound, the separated precipitate may be added to an organic solvent (for example, chloroform, toluene, hexane, n-butanol, etc.) to prepare a solution containing the semiconductor compound.

The method for producing a semiconductor compound according to the present embodiment includes a step of mixing a raw material containing: either or both of a simple substance of the metal element M and a compound containing the metal element M. In this step, the solution before heating may be added to water, or water may be added to either or both of the solution before heating and the solution during heating. Among them, water is preferably added to either one or both of the solution before heating and the solution during heating. When water is added to the solution under heating, the temperature of the solution at the time of addition is preferably 155 ℃ or lower, more preferably 150 ℃ or lower, and further preferably 140 ℃ or lower.

The amount of added water is such that the mass W of the added water _W Relative to the mass W of the metal element M contained in the raw material containing the metal element M _M Ratio (W) _W /W _M ) 0.05 to 100. The metal element M may be a metal element constituting B of the perovskite compound (1). (W) _W /W _M ) Preferably 0.05 to 3.0, more preferably 0.50 to 3.0, more preferably 1.0 to 2.2, more preferably 1.1 to 2.0. If (W) _W /W _M ) Within this range, the half width of the peak of (hkl) = (001) in the X-ray spectrum of the obtained semiconductor compound can be set within a predetermined range.

When a plurality of simple substances of the metal element M or a compound containing the metal element M are used in a raw material containing the metal element M, the W _M Can be obtained by summing up the mass sum of the simple substances of all the metal elements M used and the mass sum of the metal elements M in all the compounds containing the metal elements M used. In addition, when water is added in multiple portions, the W _W The mass of the total water added may be used.

In another aspect of this embodiment, when the metal element M is a metal element constituting B of the perovskite compound (1), W is _M The total mass of 1 or more metal elements selected from the group consisting of lead, tin, antimony, bismuth and indium contained in the perovskite compound of (1) may be used.

In another aspect of the present embodiment, the (W _W /W _M ) 0.05, 0.06, 0.07, 0.09, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8,0.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0 or more, the above (W _W /W _M ) 3.0, 2.9, 2.8, 2.7, 2.6, 2.5, 2.4, 2.3, 2.2, 2.1, 2.0, 1.9, 1.8, 1.7, 1.6, 1.5, 1.4, 1.3, 1.2, 1.1, 1.0, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1, 0.09, 0.08, 0.07, 0.06 or less.

From the viewpoint of promoting the dissolution of water in an organic solvent, it is preferable that the aqueous solution contains an ionic compound. As the ionic compound, an ammonia compound or a halide compound is preferable.

From the standpoint of promoting the dissolution of water in a solvent, it is preferable that the aqueous solution is formulated by mixing at room temperature.

In order to remove unnecessary water after the reaction and to suppress degradation, it is preferable to perform the reaction while flowing an inert gas.

In the present specification, the water content in the solution can be measured by using a trace amount of water measuring apparatus (AQ-2000, manufactured by Pingzhu industries, co., ketone electrolyte hydro-Coulomat AK).

Process for producing perovskite Compound (1)

(1) The method for producing the perovskite compound can be carried out by the method described below with reference to the prior art documents (nanolett.2015, 15, 3692-3696, ACSNano,2015,9, 4533-4542).

(method for producing 1 st)

As a method for producing the perovskite compound, a production method including: a step of dissolving the component B, the component X and the component A constituting the perovskite compound in the solvent (3) at a high temperature to obtain a solution, and a step of cooling the solution.

Hereinafter, the 1 st production method is specifically described.

First, a compound containing a component B and a component X and a compound containing a component a are dissolved in a high-temperature (3) solvent to obtain a solution. The "compound comprising component A" may also comprise component X.

The present step may be to add each compound to a solvent (3) at a high temperature to dissolve the compound, thereby obtaining a solution.

In this step, each compound may be added to the solvent (3), and then the temperature may be raised to obtain a solution. In the production method 1, the solution is preferably obtained by adding each compound to the solvent (3) and then heating the mixture.

The solvent (3) is preferably a solvent in which a compound containing a component B and a component X and a compound containing a component a are soluble as raw materials.

The "high temperature" means a solvent at a temperature at which each raw material is dissolved. For example, the temperature of the high-temperature solvent (3) is preferably 60 to 600 ℃, more preferably 80 to 400 ℃.

When the solution is obtained by adding each compound to the solvent (3) and then raising the temperature, the holding temperature after the temperature rise is, for example, preferably 80 to 150 ℃, more preferably 120 to 140 ℃.

In the production method 1, water is preferably added to the solution before or during the temperature increase.

When water is added to the solution at the temperature rise, the temperature of the solution at the time of addition is preferably 155 ℃ or lower, more preferably 150 ℃ or lower, and further preferably 140 ℃ or lower.

The amount of water added is such that the mass W of the added water _W Relative to the mass W of the metal element M contained in the raw material containing the metal element M _M Ratio (W) _W /W _M ) 0.05 to 100. (W) _W /W _M ) Preferably 0.05 to 3.0, more preferably 0.5 to 3.0, more preferably 1.0 to 2.2, more preferably 1.1 to 2.0. If (W) _W /W _M ) Within the range, then the obtained(1) The half width of the peak of (hkl) = (001) in the X-ray spectrum of the perovskite compound is within a prescribed range.

In one embodiment, (W) _W /W _M ) 0.5, 0.75, 1.0, 1.1, 1.5, 2.0, 2.2, 2.5 or more. In other modes, (W) _W /W _M ) 3.0, 2.5, 2.2, 2.0, 1.5, 1.1, 1.0, 0.75 or less.

In the present embodiment, the component B is a metal element M.

Next, the obtained solution was cooled.

In one embodiment, the cooling temperature is preferably-20 to 50 ℃, more preferably-10 to 30 ℃.

In one embodiment, the cooling temperature is-20, -15, -10, -5, 0, 5, 10, 15, 20, 25, 30, 35, 40, or 45 ℃ or higher. In other embodiments, the cooling temperature is 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 0, -5, -10, -15 ℃ or less.

The cooling rate is preferably 0.1 to 1500℃per minute, more preferably 10 to 150℃per minute.

In one embodiment, the cooling rate is 0.1, 0.5, 1, 5, 10, 25, 50, 75, 100, 150, 250, 500, 750, 1000, 1250 ℃/min or more. In other embodiments, the cooling rate is 1500, 1250, 1000, 750, 500, 250, 150, 100, 75, 50, 25, 10, 1, 0.5 ℃/min or less.

By cooling the high-temperature solution, the perovskite compound can be precipitated by the difference in solubility due to the temperature difference of the solution. Thus, a dispersion liquid containing a perovskite compound can be obtained.

The perovskite compound can be recovered by subjecting a dispersion liquid containing the obtained perovskite compound to solid-liquid separation. Examples of the method of solid-liquid separation include filtration and concentration by solvent evaporation. By performing solid-liquid separation, only the perovskite compound can be recovered.

In the above production method, the step of adding the surface modifier (6) is preferably included in order to facilitate stable dispersion of the particles of the perovskite compound obtained in the dispersion.

The step of adding the surface modifier (6) is preferably performed before the cooling step. Specifically, (6) the surface modifier may be added to the solvent of (3) or to a solution in which the compound containing the component B and the component X and the compound containing the component a are dissolved.

In the above-mentioned production method, it is preferable that the method further includes a step of removing coarse particles by centrifugation, filtration, or the like after the cooling step. The size of coarse particles removed by the removal step is preferably greater than 10. Mu.m, more preferably greater than 1. Mu.m, and even more preferably greater than 500nm.

(method for producing 2)

As a method for producing the perovskite compound, a production method including: a step of obtaining a 1 st solution containing an A component and a B component constituting a perovskite compound; a step of obtaining a 2 nd solution containing an X component constituting the perovskite compound; a step of mixing the 1 st solution and the 2 nd solution to obtain a mixed solution; and cooling the obtained mixed solution.

Hereinafter, the production method of FIG. 2 will be specifically described.

First, a compound containing a component and a compound containing B component are dissolved in the above (3) solvent at a high temperature to obtain a 1 st solution.

In this step, each compound may be added to a high-temperature solvent (3) to dissolve the compound, thereby obtaining a 1 st solution.

In this step, the 1 st solution may be obtained by adding each compound to the solvent (3) and then heating the mixture. In the production method 2, the 1 st solution is preferably obtained by adding each compound to the solvent (3) and then heating the mixture.

As the solvent (3), a solvent in which a compound containing the a component and a compound containing the B component can be dissolved is preferable.

The "high temperature" is a temperature at which the compound containing the component a and the compound containing the component B are dissolved. For example, the temperature of the high-temperature solvent (3) is preferably 60 to 600 ℃, more preferably 80 to 400 ℃.

When the 1 st solution is obtained by heating after adding each compound to the solvent (3), the holding temperature after heating is, for example, preferably 80 to 150 ℃, more preferably 120 to 140 ℃.

In one embodiment, the holding temperature after the temperature rise is 80, 90, 100, 110, 120, 130, 140 ℃ or higher. In one embodiment, the holding temperature after the temperature rise is 150, 140, 130, 120, 110, 100, 90, 80, or 70 ℃ or lower.

Further, a compound containing an X component was dissolved in the above-mentioned solvent (3), to obtain a 2 nd solution. The compound containing the X component and the compound containing the B component may be dissolved in the solvent (3) to obtain the solution 2.

The solvent (3) includes a solvent capable of dissolving a compound containing the X component.

Next, the obtained 1 st solution and 2 nd solution were mixed to obtain a mixed solution. When the 1 st solution and the 2 nd solution are mixed, one of them may be added dropwise to the other solution. In addition, the 1 st solution and the 2 nd solution may be mixed while stirring.

In the production method 2, water may be added to either or both of the 1 st solution and the 2 nd solution before or during the temperature increase, or to a mixed solution of the 1 st solution and the 2 nd solution, preferably to either or both of the 1 st solution and the 2 nd solution before or during the temperature increase, and more preferably to the 2 nd solution.

In one embodiment, when water is added to the 1 st solution at the temperature rise, the temperature of the solution at the time of addition is preferably 155 ℃ or lower, more preferably 150 ℃ or lower, and still more preferably 140 ℃ or lower.

In one embodiment, when water is added to the 2 nd solution, the temperature of the 1 st solution at the time of mixing is preferably 155 ℃ or lower, more preferably 150 ℃ or lower, and still more preferably 140 ℃ or lower.

In one embodiment, when water is added to the mixture of the 1 st solution and the 2 nd solution, the temperature of the mixture at the time of addition is preferably 155 ℃ or lower, more preferably 150 ℃ or lower, and still more preferably 140 ℃ or lower.

In one embodiment, the amount of water added is such that the mass W of the added water _W Relative to the mass W of the metal element M contained in the raw material containing the metal element M _M Ratio (W) _W /W _M ) 0.05 to 100. The metal element M may be a metal element constituting B of the perovskite compound (1). (W) _W /W _M ) Preferably 0.05 to 3.0, more preferably 0.5 to 3.0, more preferably 1.0 to 2.2, more preferably 1.1 to 2.0. If (W) _W /W _M ) Within this range, the half width of the peak of (hkl) = (001) in the X-ray spectrum of the obtained (1) perovskite compound can be set to be within a predetermined range.

In another embodiment, when a plurality of simple substances of the metal element M or a compound containing the metal element M is used in the raw material containing the metal element M, the W _M Can be obtained by summing up the mass sum of the simple substances of all the metal elements M used and the mass sum of the metal elements M in all the compounds containing the metal elements M used. In addition, when water is added in multiple portions, the W _W The mass of the total water added may be used.

In another aspect of this embodiment, the W _M Can be (1) a perovskite compound containing a structure selected from the group consisting of lead, tin, antimony, bismuth and indiumThe total mass of 1 or more metal elements in the group.

From the viewpoint of promoting the dissolution of water in an organic solvent, it is preferable that the aqueous solution contains an ionic compound. In one embodiment, the ionic compound is preferably an ammonia compound or a halide compound.

Subsequently, the obtained mixed solution was cooled.

In one embodiment, the cooling temperature is-20, -15, -10, -5, 0, 5, 10, 15, 20, or 25 ℃ or higher. In other embodiments, the cooling temperature is 30, 25, 20, 15, 10, 5, 0, -5, -10, -15 ℃ or lower.

In one embodiment, the cooling rate is preferably 0.1 to 1500℃per minute, more preferably 10 to 150℃per minute.

In one embodiment, the perovskite compound can be precipitated by cooling the mixed solution, due to the difference in solubility caused by the temperature difference of the mixed solution. Thus, a dispersion liquid containing a perovskite compound can be obtained.

In another embodiment, the perovskite compound may be recovered by subjecting the obtained dispersion liquid containing the perovskite compound to solid-liquid separation. The solid-liquid separation method includes the method shown in the production method 1.

In another aspect, in the above production method, the step of adding the surface modifier (6) is preferably included in order to facilitate stable dispersion of the particles of the obtained perovskite compound in the dispersion.

In one embodiment, the step of adding (6) the surface modifier is preferably performed before the cooling step. Specifically, (6) the surface modifier may be added to any one of (3) the solvent, the 1 st solution, the 2 nd solution, and the mixed solution.

In one aspect, the above-described manufacturing method preferably includes, after the cooling step: and removing coarse particles by a method such as centrifugation or filtration as shown in the production method 1.

Process 1 for producing composition 1

Hereinafter, for easy understanding of the properties of the obtained composition, the composition obtained in the production method 1 of the composition 1 is referred to as "composition 1-1". Composition 1-1 is a liquid composition.

In one embodiment, the composition 1-1 of the present embodiment can be produced by further mixing any one or both of (3) a solvent and (4) a polymerizable compound with (1) a perovskite compound and (2) a surface protecting agent.

In one embodiment, the perovskite compound (1) and the surface protecting agent (2) are mixed with one or both of the solvent (3) and the polymerizable compound (4), preferably with stirring.

When mixing (1) the perovskite compound and (2) the surface protecting agent with either or both of (3) the solvent and (4) the polymerizable compound, the temperature at the time of mixing is not particularly limited. In order to facilitate uniform mixing of (1) the perovskite compound and (2) the surface protecting agent, the temperature at the time of mixing is preferably in the range of 0 to 100 ℃, more preferably in the range of 10 to 80 ℃.

In one embodiment, the temperature at which the perovskite compound (1) and the surface protecting agent (2) are mixed with either or both of the solvent (3) and the polymerizable compound (4) is 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95 ℃ or higher. In another embodiment, the temperature at which the perovskite compound (1) and the surface protecting agent (2) are mixed with either or both of the solvent (3) and the polymerizable compound (4) is 100, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 25, 20, 15, 10, or 5 ℃.

(method for producing composition 1-1 containing (3) solvent)

The method for producing the composition containing (1) the perovskite compound, (2) the surface protective agent, and (3) the solvent may be, for example, the following production method (a 1) or the following production method (a 2).

Manufacturing method (a 1): a method of making a composition comprising: a step of mixing the perovskite compound (1) with the solvent (3), and a step of mixing the obtained mixture with the surface protecting agent (2).

Manufacturing method (a 2): a method of making a composition comprising: a step of mixing the perovskite compound (1) with the surface protecting agent (2), and a step of mixing the obtained mixture with the solvent (3).

The solvent (3) used in the production methods (a 1) and (a 2) is preferably a solvent in which the perovskite compound (1) is difficult to dissolve. When the solvent (3) is used, the mixture obtained in the production method (a 1) and the composition obtained in the production methods (a 1) and (a 2) become a dispersion.

When the composition of the present embodiment contains either one or both of the modified product of (2-1) silazane and the modified product of (2-2) silicon compound as (2) a surface protecting agent, the following production method (a 3) or the following production method (a 4) may be used as the production method of the composition.

Manufacturing method (a 3): a method of making a composition comprising: a step of mixing the perovskite compound (1) with the solvent (3), a step of mixing the obtained mixture with either one or both of the silazane (2-1) and the silicon compound (2-2), and a step of subjecting the obtained mixture to a modification treatment.

Manufacturing method (a 4): a method of making a composition comprising: a step of mixing (1) a perovskite compound with either one or both of the (2-1) silazane and the (2-2) silicon compound, a step of mixing the obtained mixture with (3) a solvent, and a step of subjecting the obtained mixture to a modification treatment.

The polymer (5) may also be dissolved or dispersed in the solvent (3).

In one embodiment, in the mixing step included in the above-described production method, stirring is preferably performed in order to improve dispersibility.

In the mixing step included in the above-described production method, the temperature is not particularly limited as long as mixing is possible, and is preferably in the range of 0 ℃ to 100 ℃ and more preferably in the range of 10 ℃ to 80 ℃ from the viewpoint of uniform mixing.

In one embodiment, the temperature of the mixing step included in the above-described production method is 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95 ℃ or higher. In another embodiment, the temperature of the mixing step included in the above-described production method is 100, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, or 5 ℃ or lower.

The method for producing the composition is preferably the production method (a 1) or the production method (a 3) from the viewpoint of improving the dispersibility of the perovskite compound (1).

(method of carrying out the modification treatment)

The method of the modification treatment includes known methods such as a method of irradiating ultraviolet rays to the (2-1) silazane and the (2-2) silicon compound and a method of reacting the (2-1) silazane and the (2-2) silicon compound with water vapor. In the following description, a process of reacting the (2-1) silazane and the (2-2) silicon compound with water vapor is sometimes referred to as "humidification treatment".

In one embodiment, the wavelength of ultraviolet light used in the method of irradiating ultraviolet light is usually 10 to 400nm, preferably 10 to 350nm, and more preferably 100 to 180nm. Examples of the light source for generating ultraviolet rays include a metal halide lamp, a high-pressure mercury lamp, a low-pressure mercury lamp, a xenon arc lamp, a carbon arc lamp, an excimer lamp, and an ultraviolet laser.

In one embodiment, the ultraviolet light used in the method of irradiating ultraviolet light has a wavelength of 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 150, 200, 250, 300, 350nm or more. In another embodiment, the ultraviolet light used in the method of irradiating ultraviolet light has a wavelength of 400, 390, 380, 370, 360, 350, 340, 330, 320, 310, 300, 290, 280, 270, 260, 250, 240, 230, 220, 210, 200, 190, 180, 150, 100nm or less.

Among them, it is preferable to perform the humidification treatment from the viewpoint of forming a more secure protection region in the vicinity of the perovskite compound (1).

When the humidification treatment is performed, for example, the composition may be left to stand for a certain period of time under the temperature and humidity conditions described later, or may be stirred for a certain period of time under the same conditions.

The temperature in the humidification treatment may be a temperature at which sufficient modification can be performed. The temperature in the humidification treatment is, for example, preferably 5 to 150 ℃, more preferably 10 to 100 ℃, and even more preferably 15 to 80 ℃.

In one embodiment, the temperature in the humidification treatment is 5, 10, 15, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140 ℃ or higher. In another embodiment, the temperature in the humidification process is 150, 140, 130, 120, 110, 100, 90, 80, 70, 60, 50, 40, 30, 20, 15, or 10 ℃ or lower.

The humidity in the humidification treatment may be a humidity that can sufficiently supply moisture to the (2-1) and the (2-2) in the composition. The humidity in the humidification treatment is, for example, preferably 30% to 100%, more preferably 40% to 95%, and even more preferably 60% to 90%.

The time required for the humidification treatment may be a time sufficient for the modification. The time required for the humidification treatment is, for example, preferably 10 minutes to 1 week, more preferably 1 hour to 5 days, still more preferably 2 hours to 3 days.

Stirring is preferably performed from the viewpoint of improving the dispersibility of the (2-1) and the (2-2) contained in the composition.

The water may be supplied from the interface by flowing a gas containing water vapor through the reaction vessel or by stirring in an atmosphere containing water vapor.

In one embodiment, the flow rate of the gas containing water vapor is preferably 0.01 to 100L/min, more preferably 0.1 to 10L/min, and still more preferably 0.15 to 5L/min, in order to improve the durability of the obtained composition when the gas containing water vapor is circulated in the reaction vessel. As the gas containing water vapor, for example, nitrogen gas containing a saturated amount of water vapor is cited.

In one embodiment, the flow rate of the gas including water vapor is 0.01, 0.5, 1, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90L/min or more. In another embodiment, the flow rate of the gas including water vapor is 100, 90, 80, 70, 60, 50, 40, 30, 20, 10, 5, 1, or 0.5L/min or less.

In the method for producing the composition of the present embodiment, (2) the surface protecting agent and (3) the solvent may be mixed in any of the steps included in the method for producing the perovskite compound of (1) described above. For example, the following production methods (a 5) and (a 6) may be employed.

Manufacturing method (a 5): a method of manufacture, comprising: a step of dissolving a compound containing a component B constituting a perovskite compound, a compound containing a component X, a compound containing a component A, and (2) a surface protecting agent in a high-temperature (3) solvent to obtain a solution; and cooling the solution.

Manufacturing method (a 6): a method of manufacture, comprising: a step of obtaining a 1 st solution by dissolving a compound containing an A component constituting a perovskite compound and a compound containing a B component in a high-temperature (3) solvent; a step of obtaining a 2 nd solution by dissolving a compound containing an X component constituting a perovskite compound in a solvent (3); a step of mixing the 1 st solution and the 2 nd solution to obtain a mixed solution; and cooling the obtained mixed solution.

In the production method (a 6), the (2) surface protecting agent is dissolved in either one or both of the 1 st solution and the 2 nd solution.

The conditions of each step included in these production methods are the same as those of the 1 st production method and the 2 nd production method in the above-mentioned (1) production method of the perovskite compound.

(method for producing composition 1-2 comprising (4) polymerizable Compound)

The method for producing a composition comprising (1) a perovskite compound, (2) a surface-protecting agent and (4) a polymerizable compound includes, for example, the following production methods (c 1) to (c 3).

Manufacturing method (c 1): a method of manufacture, comprising: a step of dispersing (1) a perovskite compound in (4) a polymerizable compound to obtain a dispersion; and (2) mixing the obtained dispersion with a surface protecting agent.

Manufacturing method (c 2): a method of manufacture, comprising: dispersing (2) a surface protecting agent in (4) a polymerizable compound to obtain a dispersion; and (2) mixing the obtained dispersion with the perovskite compound (1).

Manufacturing method (c 3): a method of manufacture, comprising: a step of dispersing a mixture of (1) a perovskite compound and (2) a surface protecting agent in (4) a polymerizable compound.

In one embodiment, among the production methods (c 1) to (c 3), the production method (c 1) is preferable from the viewpoint of improving the dispersibility of the perovskite compound of (1).

In the production methods (c 1) to (c 3), the polymerizable compound (4) may be added dropwise to each material or each material may be added dropwise to the polymerizable compound (4) in the step of obtaining each dispersion.

In one embodiment, at least one of (1) a perovskite compound and (2) a surface protecting agent is preferably added dropwise to (4) a polymerizable compound for ease of uniform dispersion.

In the production methods (c 1) to (c 3), the dispersion may be added dropwise to each material in each mixing step, or each material may be added dropwise to the dispersion.

In one embodiment, at least one of (1) the perovskite compound and (2) the surface protecting agent is preferably added dropwise to the dispersion for easy uniform dispersion.

At least one of (3) a solvent and (5) a polymer may be dissolved or dispersed in (4) the polymerizable compound.

The solvent for dissolving or dispersing the polymer (5) is not particularly limited. In one embodiment, the solvent is preferably a solvent in which the perovskite compound (1) is difficult to dissolve.

Examples of the solvent for dissolving the polymer (5) include the solvent (3) described above.

In one embodiment, (3) a solvent is more preferably a halogenated hydrocarbon or a hydrocarbon.

The method for producing the composition of the present embodiment may be the following production method (c 4) or the following production method (c 5).

Manufacturing method (c 4): a method for producing a composition, which comprises: dispersing the perovskite compound (1) in the solvent (3) to obtain a dispersion; a step of mixing (4) a polymerizable compound and (5) a polymer with the obtained dispersion to obtain a mixed solution; and (2) mixing the obtained mixture with a surface protecting agent.

Manufacturing method (c 5): a method for producing a composition, which comprises: dispersing the perovskite compound (1) in the solvent (3) to obtain a dispersion; a step of mixing the obtained dispersion with any one or both of the (2-1) silazane and the (2-2) silicon compound to obtain a mixed solution; a step of subjecting the obtained mixed solution to a modification treatment to obtain a mixed solution containing any one or both of the modified product of (2-1) silazane and the modified product of (2-2) silicon compound; and (3) mixing the obtained mixed solution with a solvent.

In the method 1 for producing the composition 1, when the surface modifier (6) is used, the surface protectant (2) may be added simultaneously.

Process 2 for producing composition 1

As a method for producing the composition of the present embodiment, a method for producing a composition including a step of mixing (1) a perovskite compound, (2) a surface protecting agent, and (4) a polymerizable compound, and a step of polymerizing (4) a polymerizable compound, is exemplified.

The composition obtained in the production method 2 of the composition 1 is preferably such that the total amount of (1) the perovskite compound, (2) the surface-protecting agent, and (5) the polymer is 90% by mass or more of the total composition.

The method for producing the composition of the present embodiment includes a step of mixing (1) a perovskite compound, (2) a surface protecting agent, and (5) a polymer dissolved in (3) a solvent, and a step of removing (3) the solvent.

In the mixing step included in the above production method, the same mixing method as that shown in the above production method 1 of the composition 1 can be used.

The method for producing the composition includes, for example, the following methods (d 1) and (d 2).

Manufacturing method (d 1): a method of manufacture, comprising: a step of dispersing (1) a perovskite compound and (2) a surface protecting agent in (4) a polymerizable compound, and a step of polymerizing (4) the polymerizable compound.

In the step of dispersing, the order of adding the perovskite compound (1) and the surface protecting agent (2) to the polymerizable compound (4) is not limited. The perovskite compound (1) may be added first, the surface protecting agent (2) may be added first, or the perovskite compound (1) and the surface protecting agent (2) may be added simultaneously.

Manufacturing method (d 2): a method of manufacture, comprising: a step of dispersing (1) a perovskite compound and (2) a surface protecting agent in a solvent (3) in which a polymer (5) is dissolved; and removing the solvent.

In the step of dispersing, the order of adding the perovskite compound (1) and the surface protecting agent (2) to the solvent (3) in which the polymer (5) is dissolved is not limited. The perovskite compound (1) may be added first, the surface protecting agent (2) may be added first, or the perovskite compound (1) and the surface protecting agent (2) may be added simultaneously.

The step of removing the solvent (3) included in the production method (d 2) may be a step of leaving it at room temperature and naturally drying it, or may be a step of drying it under reduced pressure using a vacuum dryer, or may be a step of evaporating the solvent (3) by heating.

In the step of removing the solvent (3), the solvent (3) may be removed by, for example, drying at 0 ℃ to 300 ℃ for 1 minute to 7 days.

The step of polymerizing the polymerizable compound (4) included in the production method (d 1) may be a known polymerization reaction such as radical polymerization.

For example, in the case of radical polymerization, a radical polymerization initiator is added to a mixture of (1) a perovskite compound, (2) a surface protecting agent, and (4) a polymerizable compound to generate radicals, thereby allowing the polymerization reaction to proceed.

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

Examples of the photo radical polymerization initiator include phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide.

In the method 2 for producing the composition 1, when the surface modifier (6) is used, the surface protectant (2) may be added simultaneously.

Process 3 for producing composition 1

The method for producing the composition of the present embodiment may be a method for producing the following (d 3) to (d 6).

Manufacturing method (d 3): a method of manufacture, comprising: and (2) a step of melt-kneading the perovskite compound (1), the surface-protecting agent (2), and the polymer (5).

Manufacturing method (d 4): a method of manufacture, comprising: a step of melt-kneading (5) a polymer and (1) one or both of a perovskite compound, the (2-1) silazane and the (2-2) silicon compound; and (3) a step of applying a humidification treatment in a state where the polymer (5) is molten.

Manufacturing method (d 5): a method of manufacture, comprising: a step of producing a liquid composition containing (1) a perovskite compound and (2) a surface-protecting agent; a step of removing a solid component from the obtained liquid composition; and (5) melt-kneading the obtained solid component with the polymer.

Manufacturing method (d 6): a method of manufacture, comprising: a step of producing a liquid composition containing the perovskite compound (1) without the surface-protecting agent (2); a step of removing a solid component from the obtained liquid composition; and (5) a step of melt-kneading the obtained solid component with (2) a surface-protecting agent and (5) a polymer.

In the production methods (d 3) to (d 6), a method known as a kneading method of a polymer can be used as a method for melt-kneading the polymer (5). For example, extrusion processing using a single screw extruder or a twin screw extruder may be employed.

The modification treatment step of the production method (d 4) may be performed by the above-described method.

The steps of producing the liquid composition according to the production methods (d 5) and (d 6) may be carried out by the production methods (a 1) or (a 2). In the step of producing the liquid composition according to the production method (d 6), the surface protecting agent (2) may not be added to the production method (a 1) or (a 2).

The step of producing the liquid composition according to the production method (d 5) may be carried out by the production method (a 3) or (a 4).

The step of taking out the solid component in the production methods (d 5) and (d 6) can be performed by, for example, heating, depressurizing, blowing, and combinations thereof, to remove the (3) solvent and (4) polymerizable compound constituting the liquid composition from the liquid composition.

In one embodiment, in the method 3 for producing a composition, when the surface modifier (6) is used, the surface protectant (2) may be added simultaneously.

Method for producing composition 2

In one embodiment, the composition 2 of the present embodiment can be produced in the same manner as the production methods 1 to 3 of the composition 1 described above, except that the addition and modification of the surface protecting agent (2) are not performed.

In one embodiment, in the method for producing a composition, when a solution containing a halide ion is added to the composition after the modification treatment, an exchange reaction between X in the perovskite compound (1) and the halide ion occurs, and the maximum emission wavelength of the perovskite compound (1) can be adjusted.

In another embodiment, after forming a surface protective layer composed of the surface protective agent (2) on the surface of the perovskite compound (1), a layer of an inorganic silicon compound having a siloxane bond may be further formed.

In the present specification, "inorganic silicon compound having a siloxane bond" means: a modified body of a compound containing an organic group and a silicon element, wherein the organic groups are organic groups which are separated by modification (hydrolysis), and a modified body of a compound containing a silicon element without an organic group.

Examples of the inorganic silicon compound having a siloxane bond include a plurality of R in the formula (B1) ¹⁵ A modified disilazane having hydrogen atoms; in the formula (B2), a plurality of R ¹⁵ A modified low molecular silazane which are all hydrogen atoms; in the above formula (B3), R is plural ¹⁵ A modified polymer silazane which is a hydrogen atom; a plurality of R in the polysilazane having the structure represented by the formula (B4) ¹⁵ A modified polymer silazane which is a hydrogen atom; sodium silicate (Na) ₂ SiO ₃ ) Is a modified product of (a).

< determination of the content of (1) perovskite Compound contained in the composition >)

The perovskite compound (1) contained in the composition of the present embodiment can be used to calculate the solid content concentration (mass%) by a dry weighing method. The dry weighing method is described in detail in the examples.

< determination of half Width of luminescence Spectrum, absorptance, luminescence wavelength >)

The half width, absorptance and emission wavelength of the emission spectrum of the perovskite compound (1) of the present invention were measured at an excitation light of 450nm, room temperature and atmosphere using an absolute PL quantum yield measuring apparatus (for example, manufactured by Hamamatsu Photonics corporation, C9920-02). The emission wavelength is the wavelength having the highest emission intensity.

In one embodiment, the excitation light absorptance of the perovskite compound (1) of the present embodiment is preferably 0.2 or more and less than 1, more preferably 0.3 or more and less than 0.9, and still more preferably 0.6 or more and less than 0.9.

In one embodiment, the perovskite compound (1) has an excitation light absorptance of 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, or 0.9 or more. In another embodiment, the perovskite compound (1) has an excitation light absorptance of 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, or 0.3 or less.

< film >

The thin film according to the present invention contains the perovskite compound (1) according to the present embodiment.

The film according to the present embodiment uses the above composition as a forming material. For example, the film according to the present embodiment contains (1) a perovskite compound and (5) a polymer, and the total of (1) the perovskite compound and (5) the polymer accounts for 90 mass% or more of the film as a whole.

The shape of the film is not particularly limited, and may be any shape such as a sheet shape, a strip shape, or the like. In the present specification, the term "stripe shape" means, for example, a shape in which a planar view extending in one direction is a stripe shape. As the shape of the band-like shape in the plane view angle, a plate-like shape having different lengths of the sides can be exemplified.

The thickness of the film may be 0.01 μm to 1000mm, may be 0.1 μm to 10mm, or may be 1 μm to 1mm.

In the present specification, the thickness of a film refers to the distance between the front surface and the back surface of the film in the thickness direction when the side having the smallest median of the length, width and height of the film is referred to as the "thickness direction". Specifically, the thickness of the film at any 3 points of the film was measured using a micrometer, and the average value of the measured values at 3 points was used as the thickness of the film.

In one embodiment, the film has a thickness of 0.01 μm, 0.5 μm, 0.1 μm, 0.5 μm, 1 μm, 5 μm, 10 μm, 25 μm, 50 μm, 75 μm, 100 μm, 250 μm, 500 μm, 750 μm, 1mm, 5mm, 10mm, 25mm, 50mm, 75mm, 100mm, 250mm, 500mm, 750mm or more. In other embodiments, the film has a thickness of 1000mm, 750mm, 500mm, 250mm, 100mm, 75mm, 50mm, 25mm, 10mm, 5mm, 1mm, 750 μm, 500 μm, 250 μm, 100 μm, 75 μm, 50 μm, 25 μm, 10 μm, 5 μm, 1 μm, 0.5 μm, 0.1 μm, or less than 0.05 μm.

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

The thin film can be obtained, for example, by a method for manufacturing a laminated structure described later. In addition, the film can be peeled from the substrate.

< laminated Structure >)

The laminated structure according to the present embodiment has a plurality of layers, and at least one layer is the film.

Among the plurality of layers included in the laminated structure, any layer other than the thin film may be used, such as a substrate, a barrier layer, and a light scattering layer.

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

(substrate)

The substrate is not particularly limited, and may be a thin film. The substrate is preferably a light-transmitting substrate. The laminated structure having the translucent substrate is preferable because light emitted from the perovskite compound (1) can be easily extracted.

As a material for forming the substrate, for example, a polymer such as polyethylene terephthalate, a known material such as glass, or the like can be used.

For example, in the laminated structure, the thin film may be provided on a substrate.

Fig. 1 is a sectional view schematically showing the structure of the laminated structure of the present embodiment. The 1 st laminated structure 1a is provided with the film 10 of the present embodiment between the 1 st substrate 20 and the 2 nd substrate 21. The film 10 is sealed by a sealing layer 22.

One side of the present invention is a laminated structure 1a, which has: the laminated structure of the 1 st substrate 20, the 2 nd substrate 21, the film 10 according to the present embodiment located between the 1 st substrate 20 and the 2 nd substrate 21, and the seal layer 22 is characterized in that the seal layer 22 is disposed on a surface of the film 10 that is not in contact with the 1 st substrate 20 and the 2 nd substrate 21.

(Barrier layer)

The layer that the laminated structure according to the present embodiment may have is not particularly limited, and examples thereof include a barrier layer. The barrier layer may also be included from the standpoint of protecting the aforementioned composition from the water vapor of the outside air and the air in the atmosphere.

The barrier layer is not particularly limited, and a transparent article is preferable from the viewpoint of taking out the emitted light. As the barrier layer, for example, a known barrier layer such as a polymer such as polyethylene terephthalate or a glass film can be used.

(light scattering layer)

The layer that the laminated structure according to the present embodiment may have is not particularly limited, and examples thereof include a light scattering layer. A light scattering layer may also be included for efficient use of the angle of the incident light.

The light scattering layer is not particularly limited, and a transparent product is preferable from the viewpoint of taking out the emitted light. As the light scattering layer, a known light scattering layer such as a light scattering particle such as a silica particle or a reinforced diffusion film can be used.

< light emitting device >

The light-emitting device according to the present invention can be obtained by combining the compound, the composition, or the laminated structure according to the embodiment of the present invention with a light source. The light-emitting device irradiates a composition or a laminated structure provided in a downstream stage with light emitted from a light source, thereby causing the compound, the composition or the laminated structure to emit light and extracting the light. Among the plurality of layers included in the laminated structure in the light-emitting device, any layer other than the thin film, the substrate, the barrier layer, and the light-scattering layer may be used, such as a light-reflecting member, a brightness enhancing portion, a prism sheet, a light guide plate, and a dielectric material layer between elements.

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

(light source)

The light source constituting the light-emitting device according to the present invention is not particularly limited, and a light source having an emission wavelength of 600nm or less is preferable in view of an angle at which the compound, the composition described above, or the perovskite compound (1) in the laminated structure emits light. As the light source, for example, a Light Emitting Diode (LED) such as a blue light emitting diode, a laser, an Electroluminescence (EL), or the like, which is known, can be used.

(light reflection member)

The layer that can be included in the laminated structure constituting the light-emitting device according to the present invention is not particularly limited, and examples thereof include light-reflecting members. The light reflecting member may be included at an angle at which the compound, composition or laminated structure described above irradiates light from the light source. The light reflecting member is not particularly limited, and may be a reflecting film.

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

(brightening part)

The layer that may be included in the laminated structure constituting the light-emitting device according to the present invention is not particularly limited, and examples thereof include a brightening portion. The brightness enhancing portion may be included at an angle that reflects a portion of the light back toward the direction of light transmission.

(prism sheet)

The layer that can be included in the laminated structure constituting the light-emitting device according to the present invention is not particularly limited, and a prism sheet is exemplified. Typically, the prism sheet has a base material portion and a prism portion. In addition, the base material portion may be omitted depending on the adjacent members. The prism sheet may be adhered to the adjacent member via any suitable adhesive layer (e.g., adhesive layer). The prism sheet is constituted by a plurality of unit prisms protruding toward the side opposite to the viewing side (back side). By disposing the convex portions of the prism sheet toward the back surface side, light transmitted through the prism sheet is easily condensed. In addition, when the prism sheet is arranged such that the convex portion faces the back surface side, light reflected without entering the prism sheet can be reduced as compared with the case where the convex portion faces the viewing side, and a display with high brightness can be obtained.

(light guide plate)

The layer that may be included in the laminated structure constituting the light-emitting device according to the present invention is not particularly limited, and examples thereof include a light guide plate. As the light guide plate, for example, any suitable light guide plate such as a light guide plate having a lens pattern formed on the back surface side, a light guide plate having a prism shape formed on the back surface side and/or the viewing side, and the like, which can deflect light in the lateral direction to the thickness direction, can be used.

(dielectric Material layer between elements)

The layer that can be included in the laminated structure constituting the light-emitting device according to the present invention is not particularly limited, and examples thereof include layers (dielectric material layers between elements) made of 1 or more dielectric materials on the optical path between adjacent elements (layers).

The medium of 1 or more types contained in the medium material layer between the elements is not particularly limited, and may include vacuum, air, gas, optical material, adhesive, optical adhesive, glass, polymer, solid, liquid, gel, cured material, optical bonding material, refractive index matching or index mismatch material, gradient refractive index material, cladding or anti-cladding material, spacer, silica gel, brightness enhancing material, scattering or diffusion material, reflection or anti-reflection material, wavelength selective anti-reflection material, color filter, or appropriate medium known in the above technical field.

Specific examples of the light-emitting device according to the present invention include devices including an Electroluminescent (EL) display and a wavelength conversion material for a liquid crystal display.

Specifically, there may be mentioned

(E1) The composition of the present invention is sealed in a glass tube or the like, and is disposed between a blue light emitting diode as a light source and the light guide plate so as to extend along an end face (side face) of the light guide plate, and a backlight (On-Edge type backlight) for converting blue light into green light or red light,

(E2) The composition of the present invention is formed into a sheet, and the sheet is sealed by sandwiching the sheet between two barrier films to form a film, the film is provided On a light guide plate, a backlight (On-Surface type backlight) for converting blue light emitted from a blue light emitting diode provided On an end face (side face) of the light guide plate, which is irradiated On the sheet through the light guide plate, into green light and red light,

(E3) A backlight (On-Chip type backlight) comprising a resin or the like dispersed in a composition of the present invention and provided in the vicinity of a light emitting portion of a blue light emitting diode to convert the irradiated blue light into green light or red light, and,

(E4) The composition of the present invention is dispersed in a resist, and is provided on a color filter, and is used as a backlight source for converting blue light emitted from a light source into green light and red light.

A specific example of the light-emitting device according to the present invention is a lighting device in which the composition according to the embodiment of the present invention is formed and arranged in a downstream section of a blue light-emitting diode as a light source, and blue light is converted into green light and red light, thereby emitting white light.

< display >

As shown in fig. 2, the display 3 of the present embodiment includes, in order from the viewing side: a liquid crystal panel 40, and the light-emitting device 2 described above. The light-emitting device 2 includes a 2 nd layered structure 1b and a light source 30. The 2 nd laminated structure 1b is formed by further providing the prism sheet 50 and the light guide plate 60 to the 1 st laminated structure 1 a. The display may further be provided with any suitable other components.

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

(liquid Crystal Panel)

In one aspect, the liquid crystal panel typically includes: the liquid crystal display device comprises a liquid crystal unit, a viewing-side polarizing plate arranged on the viewing side of the liquid crystal unit, and a back-side polarizing plate arranged on the back side of the liquid crystal unit. The viewing-side polarizing plate and the back-side polarizing plate may be arranged substantially perpendicular or parallel to their respective absorption axes.

(liquid Crystal cell)

In one embodiment, a liquid crystal cell includes: a pair of substrates, and a liquid crystal layer as a display medium sandwiched between the substrates. In a general structure, a color filter and a black matrix are provided on one substrate, and on the other substrate: a switching element for controlling the electro-optical characteristics of the liquid crystal, a scanning line for supplying a gate signal to the switching element, a signal line for supplying a source signal, a pixel electrode, and a counter electrode. The spacing (cell gap) of the substrates may be controlled by spacers or the like. An alignment film containing polyimide, for example, may be provided on the side of the substrate in contact with the liquid crystal layer.

(polarizing plate)

In one embodiment, the polarizing plate typically has a polarizer and protective layers disposed on both sides of the polarizer. The polarizer is typically an absorption type polarizer.

As the polarizer, any suitable polarizer may be used. Examples thereof include a hydrophilic polymer film such as a polyvinyl alcohol film, a partially formalized polyvinyl alcohol film, or an ethylene/vinyl acetate copolymer partially saponified film, which is obtained by adsorbing a dichroic substance such as iodine or a dichroic dye to a hydrophilic polymer film and uniaxially stretching the polymer film; a polyolefin-based oriented film such as a dehydrated product of polyvinyl alcohol or a dehydrochlorination product of polyvinyl chloride. Among these, a polarizer in which a dichroic material such as iodine is adsorbed on a polyvinyl alcohol film and uniaxially stretched is particularly preferable, and the polarizing dichroism ratio is high.

Examples of the use of the compound or the composition of the present embodiment include a wavelength conversion material for a Light Emitting Diode (LED).

＜LED＞

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

As an LED including the compound or composition of the present embodiment, for example, a structure in which the compound or composition of the present embodiment is mixed with conductive particles such as ZnS and laminated in a film shape, an n-type transport layer is laminated on one surface thereof, and a p-type transport layer is laminated on the other surface thereof, and by passing a current, holes of the p-type semiconductor and electrons of the n-type semiconductor cancel charges in particles of the perovskite compound (1) contained in the composition of the junction surface, thereby emitting light is given out.

< solar cell >)

The compound or the composition of the present embodiment can be used as an electron-transporting material contained in an active layer of a solar cell.

The structure of the solar cell is not particularly limited, and examples thereof include a fluorine-doped tin oxide (FTO) substrate, a dense layer of titanium oxide, a porous alumina layer, an active layer containing the compound or composition of the present embodiment, a hole transport layer such as 2,2', 7' -tetrakis (N, N '-di-p-methoxyaniline) -9,9' -spirobifluorene (Spiro-MeOTAD), and a silver (Ag) electrode in this order.

The dense layer of titanium oxide has the functions of electron transport, inhibiting the roughening effect of FTO, and inhibiting reverse electron transfer.

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

The compound or composition of the present embodiment contained in the active layer has functions of charge separation and electron transport.

Method for producing thin film

The method for producing the film includes, for example, the following methods (e 1) to (e 3).

Manufacturing method (e 1): a method of manufacturing a film comprising: a step of applying the liquid composition to obtain a coating film, and a step of removing (3) the solvent from the coating film.

Manufacturing method (e 2): a method of manufacturing a film comprising: a step of obtaining a coating film by applying a liquid composition containing (4) a polymerizable compound, and a step of polymerizing (4) a polymerizable compound contained in the obtained coating film.

Manufacturing method (e 3): a method for producing a film by molding the composition obtained in the above production methods (d 1) and (d 2).

Method for producing laminated structure

The method for producing the laminated structure includes, for example, the following methods (f 1) to (f 3).

Manufacturing method (f 1): a method for manufacturing a laminated structure, comprising: a step of producing a liquid composition, a step of applying the obtained liquid composition onto a substrate, and a step of removing (3) the solvent from the obtained coating film.

Manufacturing method (f 2): a method for manufacturing a laminated structure, comprising: and adhering the film to the substrate.

Manufacturing method (f 3): a method of manufacture, comprising: a step of producing a liquid composition containing (4) a polymerizable compound, a step of applying the obtained liquid composition onto a substrate, and a step of polymerizing (4) a polymerizable compound contained in the obtained coating film.

The steps for producing the liquid composition in the production methods (f 1) and (f 3) may be carried out by the production methods (c 1) to (c 4).

The step of applying the liquid composition on the substrate in the production methods (f 1) and (f 3) is not particularly limited, and known coating and application methods such as gravure coating, bar coating, printing, spray coating, spin coating, dip coating, and die coating can be used.

The step of removing the solvent (3) in the production method (f 1) may be the same step as the step of removing the solvent (3) included in the production method (d 2).

The step of polymerizing the polymerizable compound (4) in the production method (f 3) may be the same step as the step of polymerizing the polymerizable compound (4) included in the production method (d 1) described above.

In the step of adhering the film to the substrate in the production method (f 2), any adhesive may be used.

The binder is not particularly limited as long as it does not dissolve the perovskite compound (1), and a known binder can be used.

The method for manufacturing the laminated structure may further include: and a step of further adhering an optional film to the obtained laminated structure.

Examples of the film to be attached include a reflective film and a diffusion film.

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

The adhesive is not particularly limited as long as it does not dissolve the compound of the present embodiment, and a known adhesive can be used.

Method for manufacturing light-emitting device

Examples thereof include a method for producing a process including the steps of providing the light source and the compound, the composition, or the laminated structure described above on the optical path from the light source to the downstream stage.

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

Sensor

The compound or the composition of the present embodiment can be used as a material for a photoelectric conversion element (light detection element) included in a detection unit for detecting a predetermined characteristic of a part of a living body, such as an image detection unit (image sensor) for a solid-state imaging device, such as an X-ray imaging device or a CMOS image sensor, a fingerprint detection unit, a face detection unit, a vein detection unit, and an iris detection unit; a detection unit of an optical biosensor such as a pulse oximetry.

[ 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.

((1) determination of solid content concentration of perovskite Compound)

The solid content concentration of the perovskite compound in the composition obtained in example 5 was calculated by measuring the residual mass of a dispersion liquid containing the perovskite compound and the solvent obtained by re-dispersing each of them after drying at 105℃for 3 hours, and applying the measured mass to the following formula 1.

Concentration of solid component (mass%) =after drying mass ≡before drying mass x 100 formula 1

(mass of added Water M _W Is to be determined by (a) and (b) is to be determined by (b) a measurement of

Mass M of added water _W The measurement was performed using a trace moisture measuring apparatus (AQ-2000, manufactured by Pingzhou industries Co., ltd., ketone electrolyte hydraulic-Coulomat AK).

(measurement of half Width of luminescence Spectrum, absorptance and luminescence wavelength)

The half widths and emission wavelengths of the emission spectra of the compounds obtained in examples 1 to 5 and comparative example 1 were measured using an absolute PL quantum yield measuring apparatus (manufactured by Hamamatsu Photonics corporation, C9920-02) at an excitation light of 450nm at room temperature under the atmosphere.

Half width measurement of ((hkl) = (001)

The compounds obtained in examples 1 to 5 and comparative example 1 were subjected to X-ray structural diffraction (XRD, cuK alpha line)

After measurement of = 1.5458 λ, X' pert PRO MPD, spectra co., ltd, the half width of the peak of (hkl) = (001) was measured. The half width of the peak of (hkl) = (001) was calculated using the X-ray powder diffraction integrated analysis software PDXL (manufactured by Rigaku Corporation).

(measurement of average particle diameter)

The compounds obtained in examples 1 to 5 and comparative example 1 were observed by using a transmission electron microscope (JEM-2200 FS, manufactured by Japanese electric Co., ltd.). The compositions containing the compounds obtained in examples 1 to 5 and comparative example 1 were each cast on a grid with a support film dedicated to TEM, and naturally dried to obtain samples, which were observed at an acceleration voltage of 200 kV. In addition, in the field of view to be observed, energy dispersive X-ray analysis (JED-2300, manufactured by Japanese electric Co., ltd.) was performed to obtain an element distribution map.

The average particle diameters of the perovskite compounds obtained in examples 1 to 5 and comparative example 1 were calculated using Image analysis software Image J. The compounds obtained in examples 1 to 5 and comparative example 1 in the TEM images of the respective compositions were respectively converted to black and the other to white, and converted binarized images were obtained. At this time, it was compared with the element distribution diagram obtained in the TEM-EDX measurement, confirming that the positions of the detected components derived from the perovskite compounds obtained in examples 1 to 5 and comparative example 1 have been converted to black. For the binarized image, the size of the perovskite compound was measured.

The average particle diameter is calculated based on an average of the longest side lengths of particles having the randomly selected 300 perovskite compounds as cubes or cuboids.

Example 1

After mixing 25mL of oleylamine and 200mL of ethanol, the mixture was stirred while cooling with ice, 17.12mL of hydrobromic acid solution (48%) was added thereto, and then the mixture was dried under reduced pressure to obtain a precipitate.

The precipitate was washed with diethyl ether and dried under reduced pressure to obtain oleyl ammonium bromide.

After 200mL of toluene was mixed with 21g of oleyl ammonium bromide, water was added to the solution containing oleyl ammonium bromide so that the amount of water (g)/lead (g) was 0.58 relative to the mass (g) of lead in lead acetate-3 hydrate (raw material containing lead as metal element M) described later, to prepare 53.4mL of the solution containing oleyl ammonium bromide.

1.52g of lead acetate 3 hydrate, 1.56g of formamidine acetate, 160mL of solvent of 1-octadecene and 40mL of oleic acid were mixed. After stirring and heating to 130℃with nitrogen flow, 53.4mL of a solution containing the oleyl ammonium bromide and water was added. After the addition, the solution was cooled to room temperature to obtain a dispersion liquid 1 containing the perovskite compound of (1).

When the luminescence characteristics of a solution obtained by mixing 3.95mL of toluene with 1.50. Mu.L of the dispersion liquid were evaluated, the half width of the luminescence spectrum was 20.93nm, the absorption rate of excitation light was 0.65, and the luminescence wavelength was 541nm.

A solution of 200mL of the dispersion 1 was mixed with 100mL of toluene and 50mL of acetonitrile, and the mixture was filtered to separate solid from liquid. Then, the solid component after filtration was subjected to 2-pass flow washing with a mixed solution of 100mL of toluene and 50mL of acetonitrile, and filtered. Thus, the perovskite compound of (1) is obtained.

The perovskite compound of (1) thus obtained was dispersed in 100mL of toluene to obtain a dispersion 2. After casting and drying 50 μl of the dispersion 2 without a reflection plate, XRD measurement was performed, and the XRD spectrum had a peak derived from (hkl) = (001) at a position of 2θ=14 to 15 °. The half width of (hkl) = (001) was measured to be 0.272. Based on the measurement results, it was confirmed that the recovered (1) perovskite compound was a compound having a three-dimensional perovskite crystal structure. The average particle diameter as determined by TEM was 14.6nm.

Example 2

A dispersion was obtained in the same manner as in example 1, except that the water content of the solution containing oleyl ammonium bromide in the production process of the perovskite compound was set to be water (g)/lead (g) =1.13 with respect to the mass (g) of lead in lead acetate-3 hydrate (raw material containing lead as the metal element M). Half width of (hkl) = (001) is 0.232. The half width of the emission spectrum was 20.68nm, the absorption rate of excitation light was 0.72, and the emission wavelength was 541nm. The average particle diameter measured by TEM was 21.6nm.

Example 3

A dispersion was obtained in the same manner as in example 1, except that the water content of the solution containing oleyl ammonium bromide in the production process of the perovskite compound was set to be water (g)/lead (g) =1.69 with respect to the mass (g) of lead in lead acetate-3 hydrate (raw material containing lead as the metal element M). Half width of (hkl) = (001) is 0.213. The half width of the emission spectrum was 20.15nm, the absorption rate of excitation light was 0.65, and the emission wavelength was 542nm. The average particle diameter as determined by TEM was 18.4nm.

Example 4

A dispersion was obtained in the same manner as in example 1, except that the water content of the solution containing oleyl ammonium bromide in the production process of the perovskite compound was set to be water (g)/lead (g) =2.25 with respect to the mass (g) of lead in lead acetate-3 hydrate (raw material containing lead as the metal element M). Half width of (hkl) = (001) is 0.150. The half width of the emission spectrum was 20.16nm, the absorption rate of excitation light was 0.29, and the emission wavelength was 539nm. The average particle diameter as determined by TEM was 26.6nm.

Example 5

After mixing 25mL of oleylamine and 200mL of ethanol, the mixture was stirred while cooling with ice, 17.12mL of hydrobromic acid solution (48%) was added thereto, and then the mixture was dried under reduced pressure to obtain a precipitate. The precipitate was washed with diethyl ether and dried under reduced pressure to obtain oleyl ammonium bromide.

After 200mL of toluene was mixed with 21g of oleyl ammonium bromide, water was added to the solution containing oleyl ammonium bromide so that the mass (g) of water (g)/lead (g) was 1.69 with respect to the mass (g) of lead in lead acetate-3 hydrate (raw material containing lead as metal element M) described later.

1.52g of lead acetate 3 hydrate, 1.56g of formamidine acetate, 160mL of solvent of 1-octadecene and 40mL of oleic acid were mixed. After stirring and heating to 130℃with nitrogen flow, 53.4mL of a solution containing the oleyl ammonium bromide and water was added. After the addition, the solution was cooled to room temperature to obtain a dispersion 3 containing the perovskite compound of (1). The average particle diameter as determined by TEM was 18.4nm.

A solution of 200mL of the above dispersion 3 in which 100mL of toluene and 50mL of acetonitrile were mixed was filtered, and solid-liquid separation was performed. Then, the solid component after filtration was subjected to 2-pass flow washing with a mixed solution of 100mL of toluene and 50mL of acetonitrile, and filtered. Thus, the perovskite compound of (1) is obtained.

The perovskite compound of (1) thus obtained was dispersed in 100mL of toluene to obtain a dispersion 4. After casting and drying 50 μl of the dispersion 4 without a reflection plate, XRD measurement was performed, and the XRD spectrum had a peak derived from (hkl) = (001) at a position of 2θ=14 to 15 °. The half width of (hkl) = (001) was measured to be 0.213. Based on the measurement results, it was confirmed that the recovered (1) perovskite compound was a compound having a three-dimensional perovskite crystal structure.

The perovskite compound was mixed with xylene to give a solid content concentration of 0.9 mass%, and 185mL of dispersion 5 was prepared. To this was added 2 parts by mass of an organopolysiloxane (1500 Slow Cure, durazane, merck Performance Materials, inc.) to 1 part by mass of the perovskite compound in the dispersion 5. The half width of the luminescence spectrum was measured by the above method and was 20.60nm, and the luminescence wavelength was 538nm.

Comparative example 1

A dispersion was obtained in the same manner as in example 1, except that the water content of the solution containing oleyl ammonium bromide in the production process of the perovskite compound was set to be water (g)/lead (g) =0.046 with respect to the mass (g) of lead in lead acetate-3 hydrate (raw material containing lead as the metal element M). The water is not intentionally added, but is derived from water contained in the raw material.

Half width of (hkl) = (001) was calculated by the above method and was 0.600. The luminescence spectrum was measured by the above method and was 24.30nm, the absorption rate of excitation light was 0.64, and the luminescence wavelength was 535nm. The average particle diameter as determined by TEM was 13.1nm.

The results of examples 1 to 5 and comparative example 1 are shown in Table 1.

[ Table 1]

Based on the above results, it was confirmed that the perovskite compounds of examples 1 to 5 of the present invention were applied to a smaller half width of the emission spectrum than the composition of comparative example 1 to which the present invention was not applied.

Reference example 1

A backlight capable of converting blue light of a blue light-emitting diode into green light and red light was produced by sealing the compound or composition described in examples 1 to 5 in a glass tube or the like and disposing the compound or composition between the blue light-emitting diode as a light source and a light guide plate.

Reference example 2

The compound or composition described in examples 1 to 5 was formed into a sheet, and the sheet was sandwiched between 2 sheets of barrier films and sealed to form a film, and the film was placed on a light guide plate to produce a backlight capable of converting blue light emitted from a blue light emitting diode provided on an end face (side face) of the light guide plate to green light or red light by irradiating the sheet with the light guide plate.

Reference example 3

By disposing the compounds or compositions described in examples 1 to 5 near the light-emitting portion of the blue light-emitting diode, a backlight capable of converting the irradiated blue light into green light or red light was produced.

Reference example 4

The wavelength conversion material can be obtained by mixing the compounds or compositions described in examples 1 to 5 with a resist and then removing the solvent. By disposing the obtained wavelength conversion material between a blue light emitting diode as a light source and a light guide plate or at a downstream section of an OLED as a light source, a backlight capable of converting blue light of the light source into green light and red light is manufactured.

Reference example 5

An LED was obtained by mixing the compound or composition described in examples 1 to 5 with conductive particles such as ZnS, forming a film, laminating an n-type transmission layer on one surface, and laminating a p-type transmission layer on the other surface. By passing a current, the holes of the p-type semiconductor and the electrons of the n-type semiconductor cancel charges in the perovskite compound at the junction surface, and light is emitted.

Reference example 6

A dense layer of titanium oxide was laminated on the surface of a fluorine-doped tin oxide (FTO) substrate, a porous alumina layer was laminated thereon, the compounds or compositions described in examples 1 to 5 were laminated thereon, and after removal of the solvent, a hole transport layer such as 2,2', 7' -tetrakis- (N, N '-di-p-methoxyaniline) -9,9' -spirobifluorene (spira-ome tad) was laminated thereon, and a silver (Ag) layer was laminated thereon, to fabricate a solar cell.

Reference example 7

The composition of the present embodiment can be obtained by removing the solvent from the compound or composition described in examples 1 to 5 and molding the compound or composition, and by providing the composition downstream of the blue light-emitting diode, a laser diode illumination is produced that converts blue light irradiated from the blue light-emitting diode onto the composition into green light and red light, and emits white light.

Reference example 8

The composition of this embodiment can be obtained by removing the solvent from the compound or composition described in examples 1 to 5 and molding the compound or composition. By using the obtained composition as a part of the photoelectric conversion layer, a photoelectric conversion element (light detection element) material used and included in a light-sensing detection portion is manufactured. The photoelectric conversion element material is used in an optical biosensor such as an image detection unit (image sensor) for a solid-state imaging device such as an X-ray imaging device and a CMOS image sensor, a detection unit for detecting a predetermined characteristic of a part of a living body such as a fingerprint detection unit, a face detection unit, a vein detection unit, and an iris detection unit, and a pulse oximetry.

Industrial applicability

Accordingly, the compound having a perovskite crystal structure, the composition containing the compound, the thin film using the composition as a forming material, the laminated structure containing the thin film, and the light-emitting device and display having the laminated structure of the present invention can be suitably used for light-emitting applications.

The present invention also includes the following [1] to [28].

[1] A perovskite aggregate comprising a plurality of compounds having a perovskite crystal structure composed of A, B and X as constituent components, wherein the half width of the peak of the Miller index (001) in an X-ray diffraction pattern is 0.10 or more and less than 0.60.

X is a component located at each vertex of the 8-plane body centered on B in the perovskite crystal structure, and is an anion of at least one selected from the group consisting of a halide ion and a thiocyanate ion.

[2] The perovskite aggregate according to [1], wherein the half width of the peak of the Miller index (001) is 0.15 or more and less than 0.60.

[3] The perovskite aggregate according to [1], wherein the half width of the peak of the Miller index (001) is 0.15 or more and 0.28 or less.

[4] The perovskite aggregate according to any one of [1] to [3], wherein B is a 2-valent metal ion.

[5] The perovskite aggregate according to any one of [1] to [4], wherein B is a metal ion selected from the group consisting of lead ion, tin ion, antimony ion, bismuth ion and indium ion.

[6] The perovskite aggregate according to any one of [1] to [5], which is composed of one or more metal ions selected from the group consisting of lead ions, tin ions, antimony ions, bismuth ions, and indium ions.

[7] The perovskite aggregate according to any one of [1] to [6], wherein B is a lead ion.

[8] The perovskite aggregate according to any one of [1] to [7], wherein the compound is composed of one or more monovalent cations selected from the group consisting of cesium ions, organic ammonium ions and amidinium ions.

[9] The perovskite aggregate according to any one of [1] to [8], wherein X is one or more halogen ions selected from the group consisting of chloride ions, bromide ions, fluoride ions and iodide ions.

[10] The perovskite aggregate according to any one of [1] to [8], wherein X is 1 or more thiocyanate ions.

[11] The perovskite aggregate according to [9], wherein X is a bromide ion.

[12] A composition comprising: [1] the perovskite aggregate according to any one of [11], and at least one compound selected from the group consisting of (2-1) below, a modified product of (2-1) below, and a modified product of (2-2) below and (2-2) below.

(2-1) silazanes

[13] A composition comprising: [1] the perovskite aggregate according to any one of [11], and at least one selected from the group consisting of the following (3), the following (4) and the following (5).

(3) Solvent(s)

(4) Polymerizable compound

(5) Polymer

[14] The composition according to [12], which further comprises at least one selected from the group consisting of the following (3), the following (4) and the following (5).

(3) Solvent(s)

(4) Polymerizable compound

(5) Polymer

[15] A film comprising the perovskite aggregate of any one of [1] to [11 ].

[16] A film comprising the composition of any one of [12] to [14] as a forming material.

[17] A laminated structure comprising the film of [15] or [16 ].

[18] A light-emitting device comprising the laminated structure of [17 ].

[19] A display comprising the laminated structure of [17 ].

[20]A method for producing an aggregate comprising aggregating a plurality of semiconductor compounds containing a metal element M, wherein the semiconductor compounds have a half width of a peak of a crystal face Miller index (001) of 0.10 or more and less than 0.60 in an X-ray diffraction pattern, the method comprising: a step of mixing a raw material containing one or both of a simple substance of a metal element M and a compound containing the metal element M with water, wherein the water is present, and a step of reacting the raw material in the presence of the water, wherein the raw material contains one or both of the simple substance of the metal element M and the compound containing the metal element M, and the water has a mass W _W W relative to the mass of the metal element M contained in the raw material _M Ratio (W) _W /W _M ) 0.05 to 100.

[21] The production method according to [20], wherein the aggregate is a perovskite aggregate according to any one of [1] to [11 ].

[22] The production method according to [20] or [21], which comprises: and (2) a step of mixing at least one compound selected from the group consisting of (2-1) below, a modified product of (2-1) below, and a modified product of (2-2) below.

(2-1) silazanes

[23] The production method according to [20] or [21], which comprises: and (3) mixing polysilazane.

[24] The manufacturing method according to [20] or [24], further comprising: and (3) mixing at least one selected from the group consisting of the following (3), the following (4) and the following (5).

(3) Solvent(s)

(4) Polymerizable compound

(5) Polymer

[25] The production method according to [20] to [24], wherein the aggregate is a thin film-forming material.

[26] The method of [25], wherein the film is contained in a laminated structure.

[27] The method of producing [26], wherein the laminated structure is used for a light-emitting device.

[28] The production method according to [26], wherein the laminated structure is used for a display.

Claims

1. A compound having a perovskite crystal structure composed of A, B and X, wherein the half width of the peak of the Miller index (001) is 0.10 or more and less than 0.60 in an X-ray diffraction pattern, and the composition formula of the compound having the perovskite crystal structure is ABX _（3＋δ） The delta is-0.7 to 0.7,

a is a component located at each vertex of 6-plane body centering around B in perovskite crystal structure, and is 1-valent cation,

x is a component located at each vertex of the 8-plane body centering around B in the perovskite crystal structure, and is an anion of at least one selected from the group consisting of a halide ion and a thiocyanate ion,

b is a component located at the center of 6-plane bodies arranged at the apex of a and 8-plane bodies arranged at the apex of X in the perovskite crystal structure, and is a metal ion.

2. The compound according to claim 1, which has a perovskite crystal structure having A, B and X as constituent components, the half width of the peak of the crystal face miller index (001) being 0.20 to 0.50 in an X-ray diffraction pattern.

3. A composition comprising: the compound according to claim 1 or 2, and at least one compound selected from the group consisting of (2-1) below, a modified product of (2-1) below, and a modified product of (2-2) below and (2-2) below,

(2-1) silazanes

(2-2) a silicon compound having at least one group selected from the group consisting of an amino group, an alkoxy group and an alkylthio group, which is not silazane.

4. A composition comprising: the compound according to claim 1 or 2, and at least one selected from the group consisting of the following (3), the following (4) and the following (5),

(3) A solvent other than (4) a polymerizable compound and (5) a polymer

(4) Polymerizable compound

(5) A polymer which is not (4) a polymerizable compound.

5. The composition of claim 3, further comprising: at least one selected from the group consisting of the following (3), the following (4) and the following (5),

(3) A solvent other than (4) a polymerizable compound and (5) a polymer

(4) Polymerizable compound

(5) A polymer which is not (4) a polymerizable compound.

6. A film comprising the compound of claim 1 or 2.

7. A film comprising the composition according to any one of claims 3 to 5 as a forming material.

8. A laminated structure comprising the film of claim 6 or 7.

9. A light-emitting device comprising the laminated structure according to claim 8.

10. A display provided with the laminated structure of claim 8.

11. A method of manufacturing a semiconductor compound, comprising:

a step of mixing a raw material containing either or both of a simple substance of a metal element M and a compound containing the metal element M with water; the method comprises the steps of,

a step of reacting the raw materials in the presence of the water;

mass W of the water _W W relative to the mass of the metal element M contained in the raw material _M Ratio W of _W /W _M 0.05 to 100, wherein the semiconductor compound contains a metal element M, and the half width of the peak of the crystal face Miller index (001) is 0.10 or more and less than 0.60 in an X-ray diffraction pattern,

the semiconductor compound is a perovskite compound.