TWI830795B - Compositions, films, laminated structures, light-emitting devices and displays - Google Patents

Abstract

The composition of the present invention contains (1) component and (2) component, (1) Ingredients: luminescent semiconductor materials (2) Component: at least one compound or ion selected from the group consisting of tertiary amines, tertiary ammonium cations and salts formed from tertiary ammonium cations.

Description

Compositions, films, laminated structures, light-emitting devices and displays

The present invention relates to a composition, film, laminated structure, light-emitting device and display.

The industry has developed LED backlights that include blue LEDs (light-emitting diodes) and luminescent compositions. In recent years, as a luminescent compound contained in the above composition, attention has been paid to luminescent semiconductor materials (Non-Patent Document 1). [Prior technical literature] [Non-patent literature]

[Non-patent document 1] L. Protesescu, S. Yakunin, M. I. Bodnarchuk, F. Krieg, R. Caputo, C. H. Hendon, R. 2015)

[Problem to be solved by the invention]

However, when a composition containing a luminescent semiconductor material as described in Non-Patent Document 1 is used as a luminescent material, the heat resistance needs to be further improved.

The present invention was made in view of the above situation, and its object is to provide a highly heat-resistant composition containing a luminescent semiconductor material, a film using the composition, a laminated structure using the film, and a laminated structure having the above Light-emitting devices and displays. [Technical means to solve problems]

In order to solve the above-mentioned problems, the present invention has the following aspects. [1] A composition containing (1) component and (2) component, (1) Ingredients: luminescent semiconductor materials; (2) Component: at least one compound or ion selected from the group consisting of tertiary amines, tertiary ammonium cations and salts formed from tertiary ammonium cations. [2] The composition according to [1], wherein the component (1) is a perovskite compound containing A, B and X as constituent components, (A is a component located at each vertex of the hexahedron with B as the center in the perovskite crystal structure, and is a univalent cation; X represents the component located at each vertex of the octahedron centered on B in the perovskite crystal structure, and is at least one anion selected from the group consisting of halide ions and thiocyanate ions; B is the component located at the center of the hexahedron with A at the vertex and the octahedron with X at the vertex in the perovskite crystal structure, and is a metal ion). [3] The composition according to [1] or [2], further containing the component (5), (5) Component: selected from silazane, modified silazane, a compound represented by the following formula (C1), a modified form of a compound represented by the following formula (C1), and the following formula (C2) The compound represented by the following formula (C2), a modified form of the compound represented by the following formula (C2), the compound represented by the following formula (A5-51), a modified form of the compound represented by the following formula (A5-51), One or more of the group consisting of a compound represented by the following formula (A5-52), a modified form of the compound represented by the following formula (A5-52), sodium silicate, and a modified form of sodium silicate of compounds,

[Chemical 1] (In formula (C1), Y ⁵ represents a single bond, an oxygen atom or a sulfur atom; when Y ⁵ is an oxygen atom, R ³⁰ and R ³¹ each independently represent a hydrogen atom or an alkane having 1 to 20 carbon atoms. group, a cycloalkyl group with 3 to 30 carbon atoms, or an unsaturated hydrocarbon group with 2 to 20 carbon atoms; when Y ⁵ is a single bond or a sulfur atom, R ³⁰ represents a cycloalkyl group with 1 to 20 carbon atoms. Alkyl group, cycloalkyl group with 3 to 30 carbon atoms, or unsaturated hydrocarbon group with 2 to 20 carbon atoms. R ³¹ represents a hydrogen atom, alkyl group with 1 to 20 carbon atoms, 3 to 20 carbon atoms. 30 cycloalkyl group, or an unsaturated hydrocarbon group with 2 to 20 carbon atoms; in formula (C2), R ³⁰ , R ³¹ and R ³² respectively independently represent a hydrogen atom and an alkyl group with 1 to 20 carbon atoms. , a cycloalkyl group with 3 to 30 carbon atoms, or an unsaturated hydrocarbon group with 2 to 20 carbon atoms; in formula (C1) and formula (C2), the alkyl group represented by R ³⁰ , R ³¹ and R ³² , the hydrogen atoms contained in the cycloalkyl group and the unsaturated hydrocarbon group can be independently substituted with halogen atoms or amine groups; a is an integer from 1 to 3; when a is 2 or 3, the plurality of Y ⁵ present can be the same or different; when a is 2 or 3, the plural R ³⁰ present may be the same or different; when a is 2 or 3, the plural R ³² present may be the same or different; when a is 1 or 2 , the plural R ^31s that exist may be the same or different)

[Chemicalization 2] (In formula (A5-51) and formula (A5-52), A ^C is a divalent hydrocarbon group, Y ¹⁵ is an oxygen atom or a sulfur atom; R ¹²² and R ¹²³ each independently represent a hydrogen atom and a carbon number of 1 to 20 an alkyl group, or a cycloalkyl group having 3 to 30 carbon atoms, R ¹²⁴ represents an alkyl group having 1 to 20 carbon atoms, or a cycloalkyl group having 3 to 30 carbon atoms, and R ¹²⁵ and R ¹²⁶ represent independently Hydrogen atom, alkyl group with 1 to 20 carbon atoms, alkoxy group with 1 to 20 carbon atoms, or cycloalkyl group with 3 to 30 carbon atoms; alkyl and cycloalkyl groups represented by R ¹²² to R ¹²⁶ The hydrogen atoms contained can be independently substituted with halogen atoms or amine groups). [4] The composition according to any one of [1] to [3], further comprising at least one selected from the group consisting of (3) component, (4) component and (4-1) component, (3) Ingredient: solvent; (4) Ingredient: polymeric compound; (4-1) Ingredient: polymer. [5] A film using the composition according to any one of [1] to [4] as a forming material. [6] A laminated structure including the film described in [5]. [7] A light-emitting device including the laminated structure described in [6]. [8] A display having the laminated structure described in [6]. [Effects of the invention]

According to the present invention, it is possible to provide a highly heat-resistant composition containing a luminescent semiconductor material, a film using the composition, a laminated structure using the film, and a light-emitting device and a display including the laminated structure.

＜Composition＞ The luminescent semiconductor material (1) contained in the composition of this embodiment has luminescence properties. The so-called "luminescence" refers to the property of emitting light. The luminescence property is preferably a property of emitting light by excitation of electrons, more preferably a property of emitting light by excitation of electrons by excitation light. The wavelength of the excitation light may be, for example, 200 nm to 800 nm, 250 nm to 750 nm, or 300 nm to 700 nm.

The composition of this embodiment contains (1) component and (2) component. (1) Ingredients: luminescent semiconductor materials (2) Component: at least one compound or ion selected from the group consisting of tertiary amines, tertiary ammonium cations and salts formed from tertiary ammonium cations

In the following description, the component (1) may be described as "(1) semiconductor material", and the component (2) may be simply referred to as "(2) surface modifier".

(2) The surface modifier is a compound or ion that has the function of adsorbing on the surface of (1) the semiconductor material and stably dispersing the (1) semiconductor material in the composition. See below for details.

The composition of this embodiment only needs to be a composition containing (1) a semiconductor material and (2) a surface modifying agent, and may further contain components other than (1) a semiconductor material and (2) a surface modifying agent.

The composition of this embodiment contains (1) a semiconductor material and (2) a surface modification agent, and may further contain at least one selected from the group consisting of (3) component, (4) component, and (4-1) component. . (3) Ingredients: solvent (4) Ingredients: polymeric compounds (4-1) Ingredients: polymer

In the following description, (3) solvent, (4) polymerizable compound, (4-1) polymer may be collectively referred to as "dispersion medium". The composition of this embodiment can be dispersed in these dispersion media.

The composition of this embodiment can be dispersed in a dispersion medium. In this specification, "dispersion" means (1) a state in which a semiconductor material floats in a dispersion medium, or (1) a state in which a semiconductor material is suspended in a dispersion medium. In the case where (1) the semiconductor material is dispersed in the dispersion medium, part of (1) the semiconductor material may precipitate.

In the composition, the content ratio of the dispersion medium relative to the total mass of the composition is not particularly limited. From the viewpoint of improving the dispersibility of (1) the semiconductor material and improving the durability, the content ratio of the dispersion medium relative to the total mass of the composition is preferably 99.99 mass% or less, more preferably 99.9 mass% or less. Furthermore, it is more preferable that it is 99 mass % or less.

Moreover, from the viewpoint of improving durability, the content ratio of the dispersion medium relative to the total mass of the composition is preferably 0.1 mass% or more, more preferably 1 mass% or more, further preferably 10 mass% or more, and still more preferably Preferably, it is 50 mass % or more, More preferably, it is 80 mass % or more, Most preferably, it is 90 mass % or more.

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

Examples of combinations of the upper and lower limits include: 0.1 to 99.99 mass%, 1 to 99.9 mass%, 1 to 99 mass%, 10 to 99 mass%, 20 to 99 mass%, 50 to 99 Mass %, 90 to 99 mass %.

The composition of this embodiment may further contain component (5). Furthermore, see below for details on component (5). (5) Ingredients: selected from silazane, modified silazane, the compound represented by the above formula (C1), the modified form of the compound represented by the above formula (C1), and the compound represented by the above formula (C2) Compound, modified form of the compound represented by the above formula (C2), compound represented by the above formula (A5-51), modified form of the compound represented by the above formula (A5-51), the above formula (A5-52 ), one or more compounds from the group consisting of a modified form of the compound represented by the above formula (A5-52), sodium silicate, and a modified form of sodium silicate

In the following description, (5) component is called "(5) modified body group".

In the composition, the content ratio of (1) the semiconductor material relative to the total mass of the composition is not particularly limited. From the viewpoint of preventing the luminescent semiconductor material from aggregating easily and preventing concentration quenching, (1) the content ratio of the semiconductor material relative to the total mass of the composition is preferably 50 mass % or less, more preferably 1 mass % % or less, and more preferably 0.3 mass% or less. Furthermore, from the viewpoint of obtaining good luminous intensity, (1) the content ratio of the semiconductor material relative to the total mass of the composition is preferably 0.0001 mass % or more, more preferably 0.0005 mass % or more, and still more preferably 0.001 mass % %above.

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

Examples of combinations of the upper limit and the lower limit include: 0.0001 to 50 mass%, 0.0005 to 1 mass%, and 0.001 to 0.3 mass%.

(1) A composition in which the content ratio of the semiconductor material relative to the total mass of the composition is within the above range is preferable in that (1) the semiconductor material is less likely to agglomerate and the luminescence properties can be well exhibited.

In the composition, the content ratio of (2) the surface modifier relative to the total mass of the composition is not particularly limited. From the viewpoint of improving durability, (2) the content ratio of the surface modifier relative to the total mass of the composition is preferably 30 mass% or less, more preferably 1 mass% or less, and still more preferably 0.5 mass% or less. Moreover, from the viewpoint of improving the heat resistance of (1) the semiconductor material, the content is preferably 0.0001 mass% or more, more preferably 0.001 mass% or more, and still more preferably 0.01 mass% or more.

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

Examples of combinations of the upper limit and the lower limit include 0.0001 to 30 mass %, 0.001 to 1 mass %, and 0.01 to 0.5 mass %.

(2) A composition in which the content ratio of the surface modifier to the total mass of the composition is within the above range is preferable in terms of (1) the semiconductor material having excellent heat resistance.

In the composition, the content ratio of the (5) modifier group relative to the total mass of the composition is not particularly limited. From the viewpoint of improving (1) the dispersibility of the semiconductor material and improving the durability, the content ratio of (5) the modifier group relative to the total mass of the composition is preferably 30 mass % or less, more preferably 10% by mass or less, more preferably 7.5% by mass or less. Furthermore, from the viewpoint of improving durability, (1) the content ratio of the semiconductor material relative to the total mass of the composition is preferably 0.001 mass% or more, more preferably 0.01 mass% or more, and still more preferably 0.1 mass% or more. . The upper limit value and the lower limit value mentioned above can be combined arbitrarily. Examples of combinations of the upper limit and the lower limit include: 0.001 to 30 mass %, 0.001 to 10 mass %, and 0.1 to 7.5 mass %. (5) A composition in which the content ratio of the modifier group to the total mass of the composition is within the above range is preferred from the viewpoint of durability.

The composition of this embodiment may contain other components other than the above (1) to (5). For example, the composition of this embodiment may contain component (6). Furthermore, see below for details on component (6). (6) At least one compound or ion selected from the group consisting of carboxylic acid, carboxylate ion and carboxylate

In the following description, component (6) is referred to as "(6) other surface modifiers".

In the composition, the content ratio of (6) other surface modifiers relative to the total mass of the composition is not particularly limited. From the viewpoint of improving durability, (6) the content ratio of other surface modifiers relative to the total mass of the composition is preferably 30 mass% or less, more preferably 1 mass% or less, and still more preferably 0.5 mass% or less. . Moreover, from the viewpoint of improving the heat resistance of (1) the semiconductor material, the content is preferably 0.0001 mass% or more, more preferably 0.001 mass% or more, and still more preferably 0.01 mass% or more.

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

Examples of combinations of the upper limit and the lower limit include 0.0001 to 30 mass %, 0.001 to 1 mass %, and 0.01 to 0.5 mass %.

(6) A composition in which the content ratio of other surface modifiers relative to the total mass of the composition is within the above range is preferred in terms of (1) the semiconductor material having excellent heat resistance.

Furthermore, for example, the composition of this embodiment may further contain some impurities, a compound having an amorphous structure containing elements constituting (1) the semiconductor material, and a polymerization initiator.

The total content ratio of certain impurities, amorphous structural compounds containing elements constituting (1) semiconductor materials, and polymerization initiators in the composition of this embodiment is preferably 10 mass % or less relative to the total mass of the composition. , more preferably 5 mass% or less, further preferably 1 mass% or less.

Hereinafter, the (1) semiconductor material, (2) surface modification agent, (3) solvent, (4) polymerizable compound, (4-1) polymer, and (5) modified body contained in the composition of this embodiment will be described. group etc. to explain.

＜＜(1) Semiconductor materials＞＞ Examples of the (1) semiconductor material contained in the composition of this embodiment include the following (i) to (viii). (i) Semiconductor materials including Group II-VI compound semiconductors (ii) Semiconductor materials including Group II-V compound semiconductors (iii) Semiconductor materials including Group III-V compound semiconductors (iv) Semiconductor materials including Group III-IV compound semiconductors (v) Semiconductor materials including Group III-VI compound semiconductors (vi) Semiconductor materials including Group IV-VI compound semiconductors (vii) Semiconductor materials including transition metal-p-terminated compound semiconductors (viii) Semiconductor materials including compound semiconductors with perovskite structures

<(i) Semiconductor materials including Group II-VI compound semiconductors> Examples of Group II-VI compound semiconductors include compound semiconductors containing Group 2 elements and Group 16 elements of the periodic table, and compound semiconductors containing Group 12 elements and Group 16 elements of the periodic table. In addition, in this specification, the term "periodic table" means a long-period periodic table.

In the following description, a compound semiconductor containing Group 2 elements and Group 16 elements may be called "compound semiconductor (i-1)", and a compound semiconductor containing Group 12 elements and Group 16 elements may be called "compound semiconductor (i-1)". "Compound Semiconductor (i-2)".

Examples of the binary compound semiconductor among the compound semiconductors (i-1) include MgS, MgSe, MgTe, CaS, CaSe, CaTe, SrS, SrSe, SrTe, BaS, BaSe or BaTe.

Furthermore, the compound semiconductor (i-1) may also be (i-1-1) A ternary compound semiconductor containing one Group 2 element and two Group 16 elements; (i-1-2) A ternary compound semiconductor containing two Group 2 elements and one Group 16 element; (i-1-3) A quaternary compound semiconductor containing two Group 2 elements and two Group 16 elements.

Examples of the binary compound semiconductor among the compound semiconductors (i-2) include ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, HgS, HgSe or HgTe.

Furthermore, the compound semiconductor (i-2) may also be (i-2-1) A ternary compound semiconductor containing one Group 12 element and two Group 16 elements; (i-2-2) A ternary compound semiconductor containing two Group 12 elements and one Group 16 element; (i-2-3) A quaternary compound semiconductor containing two Group 12 elements and two Group 16 elements.

Group II-VI compound semiconductors may also contain elements other than Group 2 elements, Group 12 elements and Group 16 elements as doping elements.

<(ii) Semiconductor materials including Group II-V compound semiconductors> Group II-V compound semiconductors include Group 12 elements and Group 15 elements.

Examples of binary system compound semiconductors among Group II-V compound semiconductors 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 .

In addition, as a group II-V compound semiconductor, it may also be (ii-1) A ternary compound semiconductor containing one Group 12 element and two Group 15 elements; (ii-2) A ternary compound semiconductor containing two Group 12 elements and one Group 15 element; (ii-3) A quaternary compound semiconductor containing two Group 12 elements and two Group 15 elements.

Group II-V compound semiconductors may also contain elements other than Group 12 elements and Group 15 elements as doping elements.

<(iii) Semiconductor materials including Group III-V compound semiconductors> Group III-V compound semiconductors include Group 13 elements and Group 15 elements.

Examples of binary system compound semiconductors among Group III-V compound semiconductors include BP, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs, InSb, AlN, or BN.

In addition, as a group III-V compound semiconductor, it may also be (iii-1) A ternary compound semiconductor containing one Group 13 element and two Group 15 elements; (iii-2) A ternary compound semiconductor containing two Group 13 elements and one Group 15 element; (iii-3) A quaternary compound semiconductor containing two Group 13 elements and two Group 15 elements.

Group III-V compound semiconductors may also contain elements other than Group 13 elements and Group 15 elements as doping elements.

<(iv) Semiconductor materials including Group III-IV compound semiconductors> Group III-IV compound semiconductors include Group 13 elements and Group 14 elements.

Examples of binary compound semiconductors among Group III-IV compound semiconductors include B ₄ C ₃ , Al ₄ C ₃ , and Ga ₄ C ₃ .

In addition, as the Group III-IV compound semiconductor, it may also be (iv-1) A ternary compound semiconductor containing one Group 13 element and two Group 14 elements; (iv-2) A ternary compound semiconductor containing two Group 13 elements and one Group 14 element; (iv-3) A quaternary compound semiconductor containing two Group 13 elements and two Group 14 elements.

Group III-IV compound semiconductors may also contain elements other than Group 13 elements and Group 14 elements as doping elements.

<(v) Semiconductor materials including Group III-VI compound semiconductors> Group III-VI compound semiconductors include Group 13 elements and Group 16 elements.

Examples of binary system compound semiconductors among Group III-VI _compound semiconductors 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 InTe.

In addition, as a group III-group VI compound semiconductor, it may also be (v-1) A ternary compound semiconductor containing one Group 13 element and two Group 16 elements; (v-2) A ternary compound semiconductor containing two Group 13 elements and one Group 16 element; (v-3) A quaternary compound semiconductor containing two Group 13 elements and two Group 16 elements.

Group III-VI compound semiconductors may also contain elements other than Group 13 elements and Group 16 elements as doping elements.

<(vi) Semiconductor materials including Group IV-VI compound semiconductors> Group IV-VI compound semiconductors include Group 14 elements and Group 16 elements.

Examples of binary system compound semiconductors among Group IV-VI compound semiconductors include PbS, PbSe, PbTe, SnS, SnSe or SnTe.

Furthermore, as a Group IV-VI compound semiconductor, it may also be (vi-1) A ternary compound semiconductor containing one Group 14 element and two Group 16 elements; (vi-2) A ternary compound semiconductor containing two Group 14 elements and one Group 16 element; (vi-3) A quaternary compound semiconductor containing two Group 14 elements and two Group 16 elements.

Group III-VI compound semiconductors may also contain elements other than Group 14 elements and Group 16 elements as doping elements.

<(vii) Semiconductor materials including transition metal-p-terminated compound semiconductors> Transition metal-p-terminated compound semiconductors contain transition metal elements and p-terminated elements. The so-called "p-terminated elements" are elements belonging to groups 13 to 18 of the periodic table.

Examples of binary system compound semiconductors among transition metal-p-terminated compound semiconductors include NiS and CrS.

In addition, as a transition metal-p-terminated compound semiconductor, it may also be (vii-1) A ternary compound semiconductor containing one transition metal element and two p-terminal elements; (vii-2) A ternary compound semiconductor containing two transition metal elements and one p-terminal element; (vii-3) A quaternary compound semiconductor containing two transition metal elements and two p-terminal elements.

Transition metal-p-terminated compound semiconductors may also contain elements other than transition metal elements and p-terminated elements as doping elements.

Specific examples of the above-mentioned ternary compound semiconductor or quaternary compound semiconductor 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.

In the composition of this embodiment, among the above compound semiconductors, a compound semiconductor containing Cd as a Group 12 element and a compound semiconductor containing In as a Group 13 element are preferred. Furthermore, in the composition of this embodiment, among the above-mentioned compound semiconductors, a compound semiconductor containing Cd and Se and a compound semiconductor containing In and P are preferred.

The compound semiconductor containing Cd and Se is preferably any of a binary compound semiconductor, a ternary compound semiconductor, and a quaternary compound semiconductor. Among them, CdSe, which is a binary compound semiconductor, is particularly preferred.

The compound semiconductor containing In and P is preferably any of a binary compound semiconductor, a ternary compound semiconductor, and a quaternary compound semiconductor. Among them, InP, which is a binary compound semiconductor, is particularly preferred.

<(viii) Semiconductor material including a compound semiconductor having a perovskite structure> Compound semiconductors with a perovskite structure have a perovskite crystal structure containing A, B, and X as constituent components. In the following description, compound semiconductors with a perovskite structure are sometimes referred to simply as "perovskite compounds."

A is a component located at each vertex of a hexahedron centered on B in the perovskite crystal structure, and is a monovalent cation. X represents a component located at each vertex of an octahedron centered on B in the perovskite crystal structure, and is at least one anion selected from the group consisting of halide ions and thiocyanate ions. B is a component located at the center of a hexahedron with A at its vertex and an octahedron with X at its vertex in the perovskite crystal structure, and is a metal ion.

The perovskite compound containing A, B, and In the case of a three-dimensional structure, the composition formula of the perovskite compound is expressed as ABX _{(3 + δ)} . In the case of a two-dimensional structure, the composition formula of the perovskite compound is represented by A ₂ BX _{(4 + δ)} .

Here, δ is a number that can be appropriately changed to maintain charge balance with B, and is -0.7 or more and 0.7 or less. For example, when A is a monovalent cation, B is a divalent cation, and X is a monovalent anion, δ can be selected so that the perovskite compound becomes electrically neutral. The so-called perovskite compound becomes electrically neutral means that the electric charge of the perovskite compound is 0.

The perovskite compound includes an octahedron with B as the center and the vertex as X. The octagonal system is represented by BX ₆ . When the perovskite compound has a three-dimensional structure, the BX ₆ contained in the perovskite compound is located at the vertex of the octahedron (BX ₆ ) through two adjacent octahedrons (BX ₆ ) in the crystal. X to form a three-dimensional network structure.

When the perovskite compound has a two-dimensional structure, the BX ₆ contained in the perovskite compound is located in the octahedron (BX ₆ ) by two adjacent octahedrons (BX ₆ ) in the crystal. The vertices X share the ridges of the octahedron, thus forming a two-dimensional connected layer. The perovskite compound has a structure in which layers including two-dimensionally connected BX ₆ and layers including A are alternately stacked.

In this specification, the crystal structure of the perovskite compound can be confirmed by X-ray diffraction patterns.

When the perovskite compound has a three-dimensional perovskite crystal structure, a peak originating from (hkl) = (001) is usually confirmed at the position of 2θ=12~18° in the X-ray diffraction pattern. . Or the peak originating from (hkl)=(110) is confirmed at the position of 2θ=18~25°.

When the perovskite compound has a three-dimensional perovskite crystal structure, it is preferable to confirm the peak originating from (hkl) = (001) at 2θ=13 to 16°, or at 2θ=20 A peak originating from (hkl)=(110) was confirmed at the position of ~23°.

In the case where the perovskite compound has a two-dimensional perovskite crystal structure, the X-ray diffraction pattern is usually confirmed to be derived from (hkl) = (002) at the position of 2θ = 1 to 10°. peak. Furthermore, it is preferable to confirm the peak originating from (hkl)=(002) at the position of 2θ=2 to 8°.

The perovskite compound preferably has a three-dimensional structure.

(Component A) A constituting the perovskite compound is a monovalent cation. Examples of A include cesium ions, organic ammonium ions, and amidinium ions.

(organic ammonium ion) Specific examples of the organic ammonium ion of A include cations represented by the following formula (A3).

[Chemical 3]

In formula (A3), R ⁶ to R ⁹ each independently represent a hydrogen atom, an alkyl group or a cycloalkyl group. Among them, at least one of R ⁶ to R ⁹ is an alkyl group or a cycloalkyl group, and not all R ⁶ to R ⁹ are hydrogen atoms at the same time.

The alkyl groups represented by R ⁶ to R ⁹ may each independently be linear or branched. Furthermore, the alkyl groups represented by R ⁶ to R ⁹ may each independently have an amino group as a substituent.

When R ⁶ to R ⁹ are alkyl groups, the number of carbon atoms is usually 1 to 20 independently, preferably 1 to 4, more preferably 1 to 3, and still more preferably 1.

The cycloalkyl groups represented by R ⁶ to R ⁹ may each independently have an amino group as a substituent.

The number of carbon atoms of the cycloalkyl group represented by R ⁶ to R ⁹ is each independently usually 3 to 30, preferably 3 to 11, and more preferably 3 to 8. The number of carbon atoms also includes the number of carbon atoms of the substituent.

The groups represented by R ⁶ to R ⁹ are each independently preferably a hydrogen atom or an alkyl group.

When the perovskite compound contains the organic ammonium ion represented by the above formula (A3) as A, the number of alkyl groups and cycloalkyl groups that the formula (A3) may contain is preferably smaller. In addition, the number of carbon atoms of the alkyl group and cycloalkyl group that may be contained in the formula (A3) is preferably smaller. In this way, a perovskite compound with a three-dimensional structure with high luminous intensity can be obtained.

In the organic ammonium ion represented by formula (A3), the total number of carbon atoms contained in the alkyl group and cycloalkyl group represented by R ⁶ to R ⁹ is preferably 1 to 4. Furthermore, in the organic ammonium ion represented by formula (A3), it is more preferred that one of R ⁶ to R ⁹ is an alkyl group having 1 to 3 carbon atoms, and three of R ⁶ to R ⁹ are hydrogen atoms. .

Examples of the alkyl group for R ⁶ to R ⁹ include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second-butyl, third-butyl, n-pentyl, iso-butyl, etc. Pentyl, neopentyl, tertiary pentyl, 1-methylbutyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, 2,2-dimethylbutyl, 2,3- Dimethylbutyl, n-heptyl, 2-methylhexyl, 3-methylhexyl, 2,2-dimethylpentyl, 2,3-dimethylpentyl, 2,4-dimethylpentyl base, 3,3-dimethylpentyl, 3-ethylpentyl, 2,2,3-trimethylbutyl, n-octyl, isooctyl, 2-ethylhexyl, nonyl, decyl , undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl .

The cycloalkyl groups of R ⁶ to R ⁹ can each be independently exemplified by those in which a ring is formed on an alkyl group having 3 or more carbon atoms exemplified as the alkyl group of R ⁶ to R ⁹ . Examples include: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecanyl, norbisyl, isobisyl, and 1-adamantyl. , 2-adamantyl, tricyclodecyl, etc.

The organic ammonium ion represented by A is preferably CH ₃ NH ₃ ⁺ (also called methylammonium ion), C ₂ H ₅ NH ₃ ⁺ (also called ethylammonium ion) or C ₃ H ₇ NH ₃ ⁺ (also called propylammonium ion), more preferably CH ₃ NH ₃ ⁺ or C ₂ H ₅ NH ₃ ⁺ , further preferably CH ₃ NH ₃ ⁺ .

(Amidinium ion) Examples of the amidinium ion represented by A include an amidinium ion represented by the following formula (A4). (R ¹⁰ R ¹¹ N=CH-NR ¹² R ¹³ ) ⁺・・・(A4)

In formula (A4), R ¹⁰ to R ¹³ each independently represent a hydrogen atom, an alkyl group which may have an amino group as a substituent, or a cycloalkyl group which may have an amino group as a substituent.

The alkyl groups represented by R ¹⁰ to R ¹³ may independently be linear or branched. Furthermore, the alkyl groups represented by R ¹⁰ to R ¹³ may each independently have an amino group as a substituent.

The number of carbon atoms of the alkyl group represented by R ¹⁰ to R ¹³ is each independently usually 1 to 20, preferably 1 to 4, and more preferably 1 to 3.

The cycloalkyl groups represented by R ¹⁰ to R ¹³ may each independently have an amino group as a substituent.

The number of carbon atoms of the cycloalkyl group represented by R ¹⁰ to R ¹³ is each independently usually 3 to 30, preferably 3 to 11, and more preferably 3 to 8. The number of carbon atoms includes the number of carbon atoms of the substituent.

Specific examples of the alkyl group for R ¹⁰ to R ¹³ include the same groups as the alkyl groups exemplified for R ⁶ to R ⁹ . Specific examples of the cycloalkyl group for R ¹⁰ to R ¹³ include the same groups as the cycloalkyl groups exemplified for R ⁶ to R ⁹ .

The groups represented by R ¹⁰ to R ¹³ are each independently preferably a hydrogen atom or an alkyl group.

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

In the amidinium ion, the total number of carbon atoms contained in the alkyl group and cycloalkyl group represented by R ¹⁰ to R ¹³ is preferably 1 to 4, and more preferably R ¹⁰ is an alkane with 1 to 3 carbon atoms. group, R ¹¹ to R ¹³ are hydrogen atoms.

In a perovskite compound, when A is a cesium ion, an organic ammonium ion with 3 or less carbon atoms, or an amidinium ion with 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 with more than 4 carbon atoms or an amidinium ion with more than 4 carbon atoms, the perovskite compound has a two-dimensional structure and a quasi-2D structure. Either or both structures. In this case, the perovskite compound may have a two-dimensional structure or a quasi-two-dimensional structure partially or entirely in the crystal. If the two-dimensional perovskite crystal structure is stacked in multiple layers, it becomes equivalent to the three-dimensional perovskite crystal structure (Reference: P. PBoix et al., J. Phys. Chem. Lett. 2015, 6, 898 ~907 etc.).

A in the perovskite compound is preferably cesium ion or amidinium ion.

(Component B) B constituting the perovskite compound may be one or more metal ions selected from the group consisting of monovalent metal ions, divalent metal ions, and trivalent metal ions. B preferably contains a divalent metal ion, more preferably contains one or more metal ions selected from the group consisting of lead and tin, and further preferably is lead.

(component X) X constituting the perovskite compound may be at least one anion selected from the group consisting of halide ions and thiocyanate ions.

Examples of halide ions include chloride ions, bromide ions, fluoride ions, and iodide ions. X preferably contains bromide ions or iodide ions, more preferably contains bromide ions, and further preferably contains bromide ions and iodide ions.

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

X can be appropriately selected according to the desired emission wavelength.

When X is a bromide ion, the perovskite compound can emit fluorescence with a maximum intensity peak in a wavelength range usually above 480 nm, preferably above 500 nm, and more preferably above 520 nm.

In addition, when X is a bromide ion, the perovskite compound can emit fluorescence having a maximum intensity peak in a wavelength range of usually 700 nm or less, preferably 600 nm or less, and more preferably 580 nm or less. The upper limit and lower limit of the above wavelength ranges can be combined arbitrarily.

When X in the perovskite compound is a bromide ion, the peak of the emitted fluorescence is usually 480-700 nm, preferably 500-600 nm, and more preferably 520-580 nm.

When X is an iodide ion, the perovskite compound can emit fluorescence with a maximum intensity peak in a wavelength range of usually 520 nm or above, preferably 530 nm or above, and more preferably 540 nm or above.

In addition, when X is an iodide ion, the perovskite compound can emit fluorescence with a maximum intensity peak in a wavelength range of usually 800 nm or less, preferably 750 nm or less, and more preferably 730 nm or less. The upper limit and lower limit of the above wavelength ranges can be combined arbitrarily.

When X in the perovskite compound is an iodide ion, the peak of the emitted fluorescence is usually 520-800 nm, preferably 530-750 nm, and more preferably 540-730 nm.

When X is a chloride ion, the perovskite compound can emit fluorescence with a maximum intensity peak in a wavelength range of usually 300 nm or above, preferably 310 nm or above, and more preferably 330 nm or above.

In addition, when X is a chloride ion, the perovskite compound can emit fluorescence having a maximum intensity peak in a wavelength range of usually 600 nm or less, preferably 580 nm or less, and more preferably 550 nm or less. The upper limit and lower limit of the above wavelength ranges can be combined arbitrarily.

When X in the perovskite compound is a chloride ion, the peak of the emitted fluorescence is usually 300-600 nm, preferably 310-580 nm, and more preferably 330-550 nm.

(Examples of perovskite compounds with a three-dimensional structure) Preferred examples of perovskite compounds with a three-dimensional structure represented by ABX _{(3 + δ)} 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 .

Preferred examples of perovskite compounds with a three-dimensional structure include: CH 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≦0.7, 0＜δ≦0.7).

Preferred examples of perovskite compounds with a three-dimensional structure include: CH ₃ NH ₃ Pb _{(1 - a)} Na _a Br _{(3 + δ)} (0＜a≦0.7, -0.7≦δ＜0), CH ₃ NH ₃ Pb _{(1 - a)} Li _a Br _{(3 + δ)} (0＜a≦0.7, -0.7≦δ＜0).

Preferable examples of perovskite compounds with a three-dimensional structure include: CsPb _{(1 - a)} Na _a Br _{(3 + δ)} (0＜a≦0.7, -0.7≦δ＜0), CsPb _{(1 - a)} Li _a Br _{(3 + δ)} (0＜a≦0.7, -0.7≦δ＜0).

Preferred examples of perovskite compounds with a three-dimensional structure include: CH ₃ NH ₃ Pb _{(1 - a)} Na _a Br _{(3 + δ - y)} I _y (0＜a≦0.7, -0.7≦δ ＜0, 0＜y＜3), CH ₃ NH ₃ Pb _{(1 - a)} Li _a Br _{(3 + δ - y)} I _y (0＜a≦0.7, -0.7≦δ＜0, 0＜y＜ 3), CH ₃ NH ₃ Pb _{(1 - a)} Na _a Br _{(3 + δ - y)} Cl _y (0＜a≦0.7, -0.7≦δ＜0, 0＜y＜3), CH ₃ NH ₃ Pb _{(1 - a)} Li _a Br _{(3 + δ - y)} Cl _y (0＜a≦0.7, -0.7≦δ＜0, 0＜y＜3).

Preferred examples of perovskite compounds with 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≦0.7, -0.7≦δ＜0, 0＜y＜3).

Preferred examples of perovskite compounds with a three-dimensional structure include: CsPbBr ₃ , CsPbCl ₃ , CsPbI ₃ , CsPbBr _{(3 - y)} I _y (0＜y＜3), CsPbBr _{(3 - y)} Cl _y (0＜y＜3).

Preferred examples of perovskite compounds with a three-dimensional structure include: CH ₃ NH ₃ Pb _{(1 - a)} Zn _a Br ₃ (0＜a≦0.7), CH ₃ NH ₃ Pb _{(1 - a)} Al _a Br _{(3 + δ)} (0＜a≦0.7, 0≦δ≦0.7), CH ₃ NH ₃ Pb _{(1 - a)} Co _a Br ₃ (0＜a≦0.7), CH ₃ NH ₃ Pb _{(1 - a)} Mn _a Br ₃ (0＜a≦0.7), CH ₃ NH ₃ Pb _{(1 - a)} Mg _a Br ₃ (0＜a≦0.7).

Preferred examples of perovskite compounds with a three-dimensional structure include: CsPb _{(1 - a)} Zn _a Br ₃ (0＜a≦0.7), CsPb _{(1 - a)} Al _a Br _{(3 + δ)} ( 0＜a≦0.7, 0＜δ≦0.7), CsPb _{(1 - a)} Co _a Br ₃ (0＜a≦0.7), CsPb _{(1 - a)} Mn _a Br ₃ (0＜a≦0.7), CsPb _{(1 - a)} Mg _a Br ₃ (0＜a≦0.7).

Preferred examples of perovskite compounds with a three-dimensional structure include: CH ₃ NH ₃ Pb _{(1 - a)} Zn _a Br _{(3 - y)} I _y (0＜a≦0.7, 0＜y＜3) , CH ₃ NH ₃ Pb _{(1 - a)} Al _a Br _{(3 + δ - y)} I _y (0＜a≦0.7, 0＜δ≦0.7, 0＜y＜3), CH ₃ NH ₃ Pb _{(1 - a)} Co _a Br _{(3 - y)} I _y (0＜a≦0.7, 0＜y＜3), CH ₃ NH ₃ Pb _{(1 - a)} Mn _a Br _{(3 - y)} I _y (0＜ a≦0.7, 0＜y＜3), CH ₃ NH ₃ Pb _{(1 - a)} Mg _a Br _{(3 - y)} I _y (0＜a≦0.7, 0＜y＜3), CH ₃ NH ₃ Pb _{(1 - a)} Zn _a Br _{(3 - y)} Cl _y (0＜a≦0.7, 0＜y＜3), CH ₃ NH ₃ Pb _{(1 - a)} Al _a Br _{(3 + δ - y)} Cl _y (0＜a≦0.7, 0＜δ≦0.7, 0＜y＜3), CH ₃ NH ₃ Pb _{(1 - a)} Co _a Br _{(3 + δ - y)} Cl _y (0＜a≦0.7, 0＜y＜3), CH ₃ NH ₃ Pb _{(1 - a)} Mn _a Br _{(3 - y)} Cl _y (0＜a≦0.7, 0＜y＜3), CH ₃ NH ₃ Pb _{(1 - a )} Mg _a Br _{(3 - y)} Cl _y (0＜a≦0.7, 0＜y＜3).

Preferred examples of perovskite compounds with 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≦0.7, 0＜y＜3).

Among the perovskite compounds with the above three-dimensional structure, CsPbBr ₃ , CsPbBr _{(3 - y)} I _y (0＜y＜3), (H ₂ N=CH-NH ₂ )PbBr ₃ are more preferred, and even more preferred are (H ₂ N=CH-NH ₂ )PbBr ₃ .

(Examples of perovskite compounds with two-dimensional structure) Preferred examples of perovskite compounds with 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≦0.7, -0.7≦δ<0).

Preferable examples of perovskite compounds with 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≦0.7, -0.7≦δ＜0).

Preferred examples of perovskite compounds with 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≦0.7, -0.7 ≦δ<0, 0<y<4).

Preferred examples of perovskite compounds with 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≦0.7, -0.7 ≦δ<0, 0<y<4).

Preferred examples of perovskite compounds with a two-dimensional structure include: (C ₄ H ₉ NH ₃ ) ₂ PbBr ₄ and (C ₇ H ₁₅ NH ₃ ) ₂ PbBr ₄ .

Preferred examples of perovskite compounds with 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).

Preferred examples of perovskite compounds with 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≦0.7).

Preferred examples of perovskite compounds with 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≦0.7).

Preferred examples of perovskite compounds with 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≦0.7, 0＜y＜4).

Preferred examples of perovskite compounds with 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≦0.7, 0＜y＜4).

(Particle size of semiconductor material) When the (1) semiconductor material contained in the composition is in the form of particles, the average particle diameter of the particulate (1) semiconductor material (hereinafter also referred to as semiconductor particles) is not particularly limited as long as it has the effect of the present invention. . In order to maintain the crystal structure well, the average particle size of the semiconductor particles is preferably 1 nm or more. The average particle diameter of the semiconductor particles is more preferably 2 nm or more, further preferably 3 nm or more.

Furthermore, in order to prevent the semiconductor material from precipitating easily and to easily maintain required light-emitting characteristics, the average particle diameter of the semiconductor particles is preferably 10 μm or less. The average particle diameter of the semiconductor particles is more preferably 1 μm or less, further preferably 500 nm or less. Furthermore, the so-called "luminescence characteristics" refer to optical properties such as quantum yield, luminescence intensity, and color purity of converted light obtained by irradiating luminescent semiconductor particles with excitation light. Color purity can be evaluated by converting the half-maximum width of the spectrum of light.

The upper limit and the lower limit of the average particle diameter of the semiconductor particles can be combined arbitrarily. For example, the average particle diameter of the semiconductor particles is preferably from 1 nm to 10 μm, more preferably from 2 nm to 1 μm, and further preferably from 3 nm to 500 nm.

In this specification, the average particle diameter of semiconductor particles can 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 determined by measuring the maximum Ferret diameter of 20 semiconductor particles using TEM or SEM, and calculating the average maximum Ferret diameter as the arithmetic mean of the measured values. In this specification, the so-called "maximum Ferret diameter" refers to the maximum distance between two parallel straight lines sandwiching semiconductor particles in a TEM or SEM image.

The particle median diameter (D50) of the semiconductor is not particularly limited as long as it has the effect of the present invention. In order to maintain the crystal structure well, it is preferably 3 nm or more. The median diameter of the semiconductor particles is more preferably 4 nm or more, and further preferably 5 nm or more.

Furthermore, in order to prevent the semiconductor material from precipitating easily and to easily maintain required light-emitting characteristics, the median diameter (D50) of the semiconductor particles is preferably 5 μm or less. The median diameter of the semiconductor particles is more preferably 500 nm or less, further preferably 100 nm or less.

The upper limit and lower limit of the semiconductor particle median diameter (D50) can be combined arbitrarily. For example, the semiconductor particle median diameter (D50) is preferably 3 nm or more and 5 μm or less, more preferably 4 nm or more and 500 nm or less, and still more preferably 5 nm or more and 100 nm or less.

In this specification, the particle size distribution of semiconductor particles can be measured, for example, by TEM or SEM. Specifically, the maximum Ferret diameter of 20 semiconductor particles can be observed by TEM or SEM, and the median diameter (D50) can be calculated based on the distribution of the maximum Ferret diameter.

In this embodiment, only one type of the above-mentioned (1) semiconductor material may be used, or two or more types may be used in combination.

＜＜(2) Surface modifier＞＞ (2) The surface modifier is at least one compound or ion selected from the group consisting of tertiary amines, tertiary ammonium cations and salts formed from tertiary ammonium cations, and is located on (1) the semiconductor material in the composition. The surface functions as (1) a surface modifier (also called a covering ligand) for semiconductor materials. More specifically, (2) the surface modification agent preferably covers at least a portion of the surface of (1) the semiconductor material. (2) Surface Modifier As a surface modifier, the surface modifier covers (1) at least part of the surface of the semiconductor material, thereby improving the heat resistance of (1) the semiconductor material.

In this embodiment, the (2) surface modification agent covering at least part of the surface of (1) the semiconductor material can be confirmed by observing the composition using, for example, SEM or TEM. Furthermore, detailed element distribution can be analyzed by energy dispersive X-ray analysis (EDX) measurement using SEM or TEM.

＜Tertiary amine＞ Examples of the tertiary amine include those represented by the following formula (A5).

[Chemical 4]

In formula (A5), R ⁴¹ to R ⁴³ each independently represent an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group or an alkynyl group, and may each independently have a substituent. Examples of the substituent include a hydrocarbon group, an amino group, a cyano group, a mercapto group, a nitro group, and the like. The hydrogen atoms contained in R ⁴¹ to R ⁴³ may be independently substituted with halogen atoms.

The organic groups of R ⁴¹ to R ⁴³ are not particularly limited, but are preferably organic groups each independently having 20 or less carbon atoms. Furthermore, the number of carbon atoms includes the number of carbon atoms of the substituent.

Examples of the alkyl group for R ⁴¹ to R ⁴³ include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second-butyl, third-butyl, n-pentyl, iso-butyl, etc. Pentyl, neopentyl, tertiary pentyl, 1-methylbutyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, 2,2-dimethylbutyl, 2,3- Dimethylbutyl, n-heptyl, 2-methylhexyl, 3-methylhexyl, 2,2-dimethylpentyl, 2,3-dimethylpentyl, 2,4-dimethylpentyl base, 3,3-dimethylpentyl, 3-ethylpentyl, 2,2,3-trimethylbutyl, n-octyl, isooctyl, 2-ethylhexyl, n-nonyl, n- Decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl , n-nonadecyl, n-eicosyl, etc. Moreover, the above-mentioned n-alkyl group may further have an alkyl group as a side chain and may be branched.

The cycloalkyl group of R ⁴¹ to R ⁴³ may be substituted by a hydrocarbon group as long as the total number of carbon atoms is in the range of 20 or less. Examples include: cyclobutyl group which may have a substituent, cyclopentyl group which may have a substituent, and cyclopentyl group which may have a substituent. Cyclohexyl group with substituent, etc.

Examples of the aryl group of R ⁴¹ to R ⁴³ include a phenyl group which may have a substituent, a naphthyl group which may have a substituent, anthracenyl which may have a substituent, and a fluorenyl group which may have a substituent. Here, the substituent is a hydrocarbon group, and any substitution position may be substituted within the range of 20 or less carbon atoms of the entire hydrocarbon group, and there may be a plurality of substitution positions. Examples of the hydrocarbon group as a substituent include an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, an aryl group which may have a substituent, and the like.

Examples of the alkenyl group for R ⁴¹ to R ⁴³ include vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decene and undecenyl. Base, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, eicosenoyl, etc.

Examples of the alkynyl group of R ⁴¹ to R ⁴³ include: ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl, decynyl, undecanyl Alkynyl, dodecynyl, tridecynyl, tetradeynyl, pentadekynyl, hexadenyl, heptadenyl, octadenyl, nonadenyl, icosynyl, etc.

Among them, the number of carbon atoms of the organic groups of R ⁴¹ and R ⁴² is each independently preferably 10 or less, more preferably 3 or less, and particularly preferably 1. The number of carbon atoms in the organic group of R ⁴³ is preferably 3 or more, more preferably 8 or more, further preferably 16 or more.

Furthermore, the total number of carbon atoms of the organic groups of R ⁴¹ to R ⁴³ is preferably 50 or less, more preferably 30 or less, still more preferably 25 or less. If the total number of carbon atoms of the organic groups of R ⁴¹ to R ⁴³ is less than the above upper limit, the size of the tertiary amine becomes suitable for covering (1) the semiconductor material, and as a result (1) the heat resistance of the semiconductor material is improved.

R ⁴¹ to R ⁴³ are particularly preferably linear alkyl groups. That is, the organic groups of R ⁴¹ and R ⁴² are each independently preferably an n-alkyl group having 10 or less carbon atoms, more preferably an n-alkyl group having 3 or less carbon atoms, and particularly preferably a methyl group. Furthermore, the organic group of R ⁴³ is preferably an n-alkyl group having 3 or more carbon atoms, more preferably an n-alkyl group having 8 or more carbon atoms, and even more preferably an n-alkyl group having 16 or more carbon atoms.

As such a combination of R ⁴¹ , R ⁴² , and R ⁴³ , it is preferred that R ⁴¹ and R ⁴² are each independently an alkyl group selected from the group consisting of methyl, ethyl, and n-propyl, and R ⁴³ is An alkyl group selected from the group consisting of n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, and n-eicosanyl.

Examples of the compound of formula (A5) include N-n-octyldimethylamine, N,N-dimethyldecylamine, N,N-dimethyllaurylamine, and N,N-dimethylamine. Myristylamine, N,N-dimethylhexadecylamine, N,N-dimethylstearylamine, N,N-dimethyln-octadecylamine, didecylmethylamine , N,N-di-n-octylmethylamine, triheptylamine, N-methyldi-dodecylamine, tri-n-octylamine, trinonylamine, from the perspective of improving durability, Preferred are N-n-octyldimethylamine, N,N-dimethyldecylamine, N,N-dimethyllaurylamine, N,N-dimethylmyristylamine, N,N -Dimethylhexadecylamine, N,N-dimethylstearylamine, N,N-dimethyln-octadecylamine, preferably N,N-dimethyln-octadecane base amine.

＜Tertiary ammonium cations, salts formed from tertiary ammonium cations＞ Examples of the tertiary ammonium cation include the tertiary ammonium cation represented by the following formula (A6). In the composition of this embodiment, when (1) the semiconductor material is a perovskite compound, the component A of the perovskite compound is different from the tertiary ammonium cation as (2) the surface modification agent.

[Chemistry 5]

In the above formula (A6), R ⁴¹ to R ⁴³ represent the same groups as R ⁴¹ to R ⁴³ contained in the above formula (A5).

When the tertiary ammonium cation represented by the above formula (A6) forms a salt, the counter anion is not particularly limited. As the counter anion, halide ions, carboxylate ions, etc. are preferred. Examples of halide ions include bromide ions, chloride ions, iodide ions, and fluoride ions.

In this embodiment, only one type of the above-mentioned (2) surface modifying agent may be used, or two or more types may be used in combination.

＜＜(6)Other surface modification agents＞＞ (6) Other surface modifiers are at least one compound or ion selected from the group consisting of carboxylic acid, carboxylate ion and carboxylate.

(6) The other surface modifier is a surface modifier other than the above-mentioned (2) surface modifier. In the composition of this embodiment, it is located on the surface of (1) the semiconductor material and functions as a surface modifier of (1) the semiconductor material. its role. More specifically, (6) other surface modification agents preferably cover at least part of the surface of (1) the semiconductor material. (6) Other surface modifiers serve as surface modifiers to cover (1) at least part of the surface of the semiconductor material, thereby (1) improving the heat resistance of the semiconductor material.

In this embodiment, (6) other surface modifiers covering at least part of the surface of (1) the semiconductor material can be confirmed by observing the composition using, for example, SEM or TEM. Furthermore, detailed element distribution can be analyzed by EDX measurement using SEM or TEM.

<Carboxylic acid, carboxylate ion, carboxylate> The carboxylate ion as a surface modifier is represented by the following formula (A2). The carboxylic acid salt as a surface modification agent is a salt containing an ion represented by the following formula (A2). R ^5- CO ₂ ^-・・・(A2)

Examples of carboxylic acids used as surface modifiers include carboxylic acids in which a proton (H ⁺ ) is bonded to the carboxylic acid ester anion represented by (A2).

In the ion represented by formula (A2), R ⁵ represents a monovalent hydrocarbon group. The hydrocarbon group represented by R ⁵ 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.

The alkyl group represented by R ⁵ may be linear or branched.

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

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

The number of carbon atoms of the unsaturated hydrocarbon group represented by R ⁵ is usually 2 to 20, preferably 5 to 20, and more preferably 8 to 20.

R ⁵ is preferably an alkyl group or an unsaturated hydrocarbon group. As the unsaturated hydrocarbon group, an alkenyl group is preferred.

Specific examples of the alkyl group for R ⁵ include the alkyl groups exemplified for R ⁶ to R ⁹ . Specific examples of the cycloalkyl group of R ⁵ include the cycloalkyl groups exemplified for R ⁶ to R ⁹ .

Specific examples of the alkenyl group of R ⁵ include vinyl, propenyl, 3-butenyl, 2-butenyl, 2-pentenyl, 2-hexenyl, 2-nonenyl, 2 -Dodecenyl, 9-octadecenyl.

The carboxylate anion represented by formula (A2) is preferably an oleate anion.

When the carboxylic acid ester anion forms a salt, the counter cation is not particularly limited, and preferred examples include alkali metal cations, alkaline earth metal cations, ammonium cations, and the like.

The carboxylic acid used as the surface modification agent is preferably oleic acid. ＜＜(3) Solvent＞＞ The solvent (3) contained in the composition of this embodiment is not particularly limited as long as it is a medium that can disperse the semiconductor material (1). The solvent contained in the composition of this embodiment is preferably one that is difficult to dissolve (1) the semiconductor material.

In this specification, the so-called "solvent" refers to a substance that is in a liquid state at 1 atmosphere and 25°C. The solvent does not include polymerizable compounds and polymers described below.

Examples of the solvent include the following (a) to (k). (a): Esters (b): Ketones (c): ether (d): alcohol (e): Glycol ether (f): Organic solvent with amide group (g): Organic solvent with nitrile group (h): Organic solvent with carbonate group (i): Halogenated hydrocarbons (j): Hydrocarbon (k): dimethyl sulfoxide

Examples of the (a) ester include methyl formate, ethyl formate, propyl formate, pentyl formate, methyl acetate, ethyl acetate, and pentyl acetate.

Examples of (b) ketones include γ-butyrolactone, N-methyl-2-pyrrolidone, acetone, diisobutyl ketone, cyclopentanone, cyclohexanone, methylcyclohexanone, and the like.

Examples of (c) ethers include diethyl ether, methyl tert-butyl ether, diisopropyl ether, dimethoxymethane, dimethoxyethane, 1,4-dioxane, and 1,3-diisopropyl ether. Oxolane, 4-methyldioxolane, tetrahydrofuran, methyltetrahydrofuran, anisole, phenethyl ether, etc.

Examples of (d) alcohol include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, tert-butanol, 1-pentanol, and 2-methyl-2- Butanol, methoxypropanol, diacetone alcohol, cyclohexanol, 2-fluoroethanol, 2,2,2-trifluoroethanol, 2,2,3,3-tetrafluoro-1-propanol, etc.

Examples of (e) glycol ethers include 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 (f) the organic solvent having a amide group include N,N-dimethylformamide, acetamide, N,N-dimethylacetamide, and the like.

Examples of (g) the organic solvent having a nitrile group include acetonitrile, isobutyronitrile, propionitrile, methoxyacetonitrile, and the like.

Examples of (h) the organic solvent having a carbonate group include ethylene carbonate, propylene carbonate, and the like.

Examples of (i) halogenated hydrocarbons include methylene chloride, chloroform, and the like.

Examples of (j) hydrocarbons include n-pentane, cyclohexane, n-hexane, 1-octadecene, benzene, toluene, xylene, and the like.

Among these solvents, (a) ester, (b) ketone, (c) ether, (g) organic solvent with nitrile group, (h) organic solvent with carbonate group, (i) halogenated hydrocarbon and (j) ) Hydrocarbons are preferred because they have low polarity and are difficult to dissolve (1) semiconductor materials.

Furthermore, as the solvent used in the composition of this embodiment, (i) halogenated hydrocarbons and (j) hydrocarbons are more preferred.

In the composition of this embodiment, only one type of the above-mentioned solvent may be used, or two or more types may be used in combination.

＜＜(4)Polymerizable compound＞＞ The (4) polymerizable compound contained in the composition of this embodiment is preferably one that is difficult to dissolve the (1) semiconductor material of this embodiment at the temperature at which the composition of this embodiment is produced.

In this specification, the "polymerizable compound" means a monomer compound (monomer) having a polymerizable group. Examples of the polymerizable compound include monomers that are in a liquid state at 1 atmosphere and 25°C.

For example, when the composition is produced at room temperature and normal pressure, the polymerizable compound is not particularly limited. Examples of the polymerizable compound include known polymerizable compounds such as styrene, acrylate, methacrylate, and acrylonitrile. Among these, the polymerizable compound is preferably any one or both of acrylate and methacrylate which are monomers of acrylic resin.

In the composition of this embodiment, only one type of polymerizable compound may be used, or two or more types may be used in combination.

In the composition of this embodiment, the ratio of the total amount of acrylate and methacrylate to the entire polymerizable compound (4) may be 10 mol% or more. The same ratio may be 30 mol% or more, 50 mol% or more, 80 mol% or more, or 100 mol%.

＜＜(4-1)Polymer＞＞ The polymer contained in the composition of this embodiment is preferably a polymer with a low solubility of the (1) semiconductor material of this embodiment at the temperature at which the composition of this embodiment is produced.

For example, when the composition is produced at room temperature and normal pressure, the polymer is not particularly limited, and examples thereof include well-known polymers such as polystyrene, acrylic resin, and epoxy resin. Among them, as the polymer, an acrylic resin is preferred. The acrylic resin contains any one or both of a structural unit derived from an acrylic acid ester and a structural unit derived from a methacrylic acid ester.

In the composition of this embodiment, the ratio of the total amount of structural units derived from acrylic acid ester and structural units derived from methacrylic acid ester to all structural units contained in the polymer (4-1) may be 10 mol%. above. The same ratio may be 30 mol% or more, 50 mol% or more, 80 mol% or more, or 100 mol%.

(4-1) The weight average molecular weight of the polymer is preferably 100 to 1,200,000, more preferably 1,000 to 800,000, and even more preferably 5,000 to 150,000.

In this specification, the "weight average molecular weight" means a polystyrene-converted value measured by gel permeation chromatography (GPC).

In this embodiment, only one type of the polymer (4-1) mentioned above may be used, or two or more types may be used in combination.

＜＜(5) Modified body group＞＞ (5) The modified group is selected from silazane, modified silazane, a compound represented by formula (C1) to be described later, a modified form of a compound represented by formula (C1), and a compound represented by formula (C2) to be described later. The compound represented by the formula (C2), a modified form of the compound represented by the formula (C2), the compound represented by the formula (A5-51) described below, the modified form of the compound represented by the formula (A5-51), the compound represented by the formula (A5-52) described below ), one or more compounds from the group consisting of a compound represented by formula (A5-52), a modified form of the compound represented by formula (A5-52), sodium silicate, and a modified form of sodium silicate.

In the composition, (5) the modified body group preferably forms a shell structure with (1) semiconductor material coated with (2) surface modifier as a core. Specifically, the (5) modifier group is preferably coated on at least a part of the surface of the (2) surface modifier that covers the (1) surface of the semiconductor material, or may be coated on the surface without the (2) surface modifier. At least part of the surface of (1) the semiconductor material covered.

In this embodiment, the (5) modified body group that covers at least part of the surface of (1) the semiconductor material or (2) the surface modifying agent can be confirmed by observing the composition using, for example, SEM or TEM. Furthermore, detailed element distribution can be analyzed by EDX measurement using SEM or TEM.

In this specification, "modification" means the hydrolysis of silicon compounds with Si-N bonds, Si-SR bonds (R is a hydrogen atom or an organic group) or Si-OR bonds (R is a hydrogen atom or an organic group). A silicon compound with Si-O-Si bonds is generated. Si-O-Si bonds can be formed by condensation reactions between molecules or by condensation reactions within molecules.

In this specification, "modified body" means a compound obtained by modifying a silicon compound having a Si-N bond, a Si-SR bond, or a Si-OR bond.

(1. Silazane) Silazane is a compound having Si-N-Si bonds. Silazane may be linear, branched, or cyclic.

The silazane can be a low molecular weight silazane or a high molecular weight silazane. In this specification, polymer silazane may be referred to as polysilazane.

In this specification, the so-called "low molecular weight" means that the number average molecular weight is less than 600. In addition, in this specification, "polymer" means a number average molecular weight of 600 to 2,000.

In this specification, the "number average molecular weight" means a polystyrene-converted value measured by gel permeation chromatography (GPC).

(1-1. Low molecular weight silazane) As the silazane, for example, disilazane represented by the following formula (B1) as a low molecular weight silazane is preferred.

[Chemical 6]

In formula (B1), R ¹⁴ and R ¹⁵ each independently represent 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, or a carbon atom. An aryl group having 6 to 20 atoms, or an alkylsilyl group having 1 to 20 carbon atoms.

R ¹⁴ and R ¹⁵ may have substituents such as an amino group. The plural R ^15s that exist may be the same or different.

Examples of the low molecular weight silazane represented by the formula (B1) include: 1,3-divinyl-1,1,3,3-tetramethyldisilazane, 1,3-diphenyltetramethyl 1,1,1,3,3,3-hexamethyldisilazane.

(1-2. Low molecular weight silazane) As the silazane, for example, a low molecular weight silazane represented by the following formula (B2) is also preferred.

[Chemical 7]

In the formula (B2), R ¹⁴ and R ¹⁵ are the same as R ¹⁴ and R ¹⁵ in the above formula (B1).

The plural R ^14s that exist may be the same or different. The plural R ^15s that exist may be the same or different.

In formula (B2), n ₁ represents an integer from 1 to 20. n ₁ can be an integer from 1 to 10, and can be 1 or 2.

Examples of the low molecular weight silazane represented by formula (B2) include: octamethylcyclotetrasilazane, 2,2,4,4,6,6-hexamethylcyclotrisilazane and 2,4 ,6-trimethyl-2,4,6-trivinylcyclotrisilazane.

As the low molecular weight silazane, octamethylcyclotetrasilazane and 1,3-diphenyltetramethyldisilazane are preferred, and octamethylcyclotetrasilazane is more preferred.

(1-3.Polymer silazane) As the silazane, for example, a polymer silazane (polysilazane) represented by the following formula (B3) is preferred.

Polysilazane is a polymer compound with Si-N-Si bonds. The structural unit of the polysilazane represented by formula (B3) may be one type or a plurality of types.

[Chemical 8]

In the formula (B3), R ¹⁴ and R ¹⁵ are the same as R ¹⁴ and R ¹⁵ in the above formula (B1).

In formula (B3), * represents a bonding bond. R ¹⁴ is bonded to the bond of the N atom at the end of the molecular chain. R ¹⁵ is bonded to the bond of the Si atom at the end of the molecular chain.

The plural R ^14s that exist may be the same or different. The plural R ^15s that exist may be the same or different.

m represents an integer from 2 to 10,000.

The polysilazane represented by formula (B3) may be, for example, a perhydrogen polysilazane in which R ¹⁴ and R ¹⁵ are both hydrogen atoms.

Furthermore, the polysilazane represented by formula (B3) may be, for example, an organic polysilazane in which at least one R ¹⁵ is a group other than a hydrogen atom. Perhydropolysilazane and organopolysilazane can be appropriately selected according to the application, or they can be mixed and used.

(1-4.Polymer silazane) As the silazane, for example, polysilazane having a structure represented by the following formula (B4) is also preferred.

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

[Chemical 9]

In formula (B4), * represents a bonding bond. The bond of the formula (B4) can be bonded to the bond of the polysilazane represented by the formula (B3) or the bond of the structural unit of the polysilazane represented by the formula (B3).

In addition, when the polysilazane contains a plurality of structures represented by formula (B4) in the molecule, the bonding bond of the structure represented by formula (B4) may be bonded with other structures represented by formula (B4). The bonding bond is bonded directly.

In the bond with the polysilazane represented by the formula (B3), the bond with the structural unit of the polysilazane represented by the formula (B3), and the bond with other structures represented by the formula (B4) R ¹⁴ is bonded to the bond of the N atom that is not bonded to any of the bonds.

In the bond with the polysilazane represented by the formula (B3), the bond with the structural unit of the polysilazane represented by the formula (B3), and the bond with other structures represented by the formula (B4) R ¹⁵ is bonded to the bond of the Si atom that is not bonded to any of the bonds.

n ₂ represents an integer from 1 to 10,000. n ₂ can be an integer from 1 to 10, and can be 1 or 2.

General polysilazane has, for example, a structure in which a linear structure and a ring structure such as a 6-membered ring or an 8-membered ring exist, that is, the structures represented by the above (B3) and (B4). The molecular weight of general polysilazane is about 600 to 2000 in terms of number average molecular weight (Mn) (converted to polystyrene). Depending on the molecular weight, it can be a liquid or a solid substance.

Commercially available polysilazane can also be used. Examples of commercially available products include: NN120-10, NN120-20, NAX120-20, NN110, NAX120, NAX110, NL120A, NL110A, NL150A, NP110, NP140 (AZ ELECTRONIC MATERIALS Co., Ltd.), and AZNN-120-20, Durazane (registered trademark) 1500 Slow Cure, Durazane 1500 Rapid Cure, Durazane 1800 and Durazane 1033 (manufactured by Merck Performance Materials Co., Ltd.), etc.

Preferable polysilazane is AZNN-120-20, Durazane 1500 Slow Cure, Durazane 1500 Rapid Cure, more preferably Durazane 1500 Slow Cure, Durazane 1500 Rapid Cure, and still more preferably Durazane 1500 Rapid Cure.

Regarding the modified low-molecular silazane represented by formula (B2), the ratio of silicon atoms not bonded to nitrogen atoms is preferably 0.1 to 100% relative to all silicon atoms. Furthermore, the ratio of silicon atoms not bonded to nitrogen atoms is more preferably 10 to 98%, and further preferably 30 to 95%.

Furthermore, "the ratio of silicon atoms not bonded to nitrogen atoms" can be measured using the following measurement value, by ((Si (mol) - (N (mol) in SiN bond)/Si (mol) It is determined by

Regarding the modified polysilazane represented by formula (B3), the ratio of silicon atoms not bonded to nitrogen atoms is preferably 0.1 to 100% relative to all silicon atoms. Furthermore, the ratio of silicon atoms not bonded to nitrogen atoms is more preferably 10 to 98%, and further preferably 30 to 95%.

Regarding the modified polysilazane having a structure represented by formula (B4), the ratio of silicon atoms not bonded to nitrogen atoms is preferably 0.1 to 99% relative to all silicon atoms. Furthermore, the ratio of silicon atoms not bonded to nitrogen atoms is more preferably 10 to 97%, and further preferably 30 to 95%.

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

Regarding the modified body, the "ratio of silicon atoms not bonded to nitrogen atoms" calculated using the measured value obtained by the above method is preferably 0.1 to 99%, more preferably 10 to 99%, and still more preferably It is 30~95%.

The silazane or its modified form contained in (5) the modified group is not particularly limited. From the viewpoint of improving dispersion and suppressing aggregation, organopolysilazane or its modified form is preferred. body.

Examples of the organopolysilazane include those represented by formula (B3), in which at least one of R ¹⁴ and R ¹⁵ is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, or a carbon atom. Organopolysilazane having a cycloalkyl group with 3 to 20 carbon atoms, an aryl group with 6 to 20 carbon atoms, or an alkylsilyl group with 1 to 20 carbon atoms.

Furthermore, the organopolysilazane may have a structure represented by formula (B4), for example, in which at least one bond is bonded to R ¹⁴ or R ¹⁵ , and at least one of R ¹⁴ and R ¹⁵ is a carbon atom. Alkyl group with 1 to 20 carbon atoms, alkenyl group with 1 to 20 carbon atoms, cycloalkyl group with 3 to 20 carbon atoms, aryl group with 6 to 20 carbon atoms, or alkylsilyl group with 1 to 20 carbon atoms. of organopolysilazane.

The organopolysilazane is preferably an organopolysilazane represented by formula (B3) and at least one of R ¹⁴ and R ¹⁵ is a methyl group, or an organopolysilazane having a structure represented by formula (B4) and at least one bond A polysilazane in which R ¹⁴ or R ¹⁵ is bonded and at least one of R ¹⁴ and R ¹⁵ is a methyl group.

(2. Compounds represented by formula (C1), compounds represented by formula (C2)) As the modified group (5), compounds represented by the following formula (C1) and compounds represented by the following formula (C2) may also be used.

[Chemical 10]

In formula (C1), Y ⁵ represents a single bond, an oxygen atom or a sulfur atom.

When Y ⁵ is an oxygen atom, R ³⁰ and R ³¹ each independently represent a hydrogen atom, an alkyl group with a carbon number of 1 to 20, a cycloalkyl group with a carbon number of 3 to 30, or a carbon number of 2 to 20 unsaturated hydrocarbon groups.

When Y ⁵ is a single bond or a sulfur atom, R ³⁰ represents an alkyl group with 1 to 20 carbon atoms, a cycloalkyl group with 3 to 30 carbon atoms, or an unsaturated hydrocarbon group with 2 to 20 carbon atoms. , R ³¹ represents a hydrogen atom, an alkyl group with 1 to 20 carbon atoms, a cycloalkyl group with 3 to 30 carbon atoms, or an unsaturated hydrocarbon group with 2 to 20 carbon atoms.

In formula (C2), R ³⁰ , R ³¹ , and R ³² each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, or 2 carbon atoms. ~20 unsaturated hydrocarbon groups.

In the formulas (C1) and (C2), the hydrogen atoms contained in the alkyl group, cycloalkyl group and unsaturated hydrocarbon group represented by R ³⁰ , R ³¹ and R ³² may be independently substituted with a halogen atom or an amino group.

Examples of the halogen atom that can substitute for the hydrogen atom contained in the alkyl group, cycloalkyl group, and unsaturated hydrocarbon group represented by R ³⁰ , R ³¹ , and R ³² include: fluorine atom, chlorine atom, bromine atom, and iodine atom , from the viewpoint of chemical stability, a fluorine atom is preferred.

In formulas (C1) and (C2), a is an integer from 1 to 3. When a is 2 or 3, the plural Y ⁵ that exist may be the same or different. When a is 2 or 3, the plural R ^30s that exist may be the same or different. When a is 2 or 3, the existing plural R ³² may be the same or different. When a is 1 or 2, the plural R ^31s that exist may be the same or different.

The alkyl group represented by R ³⁰ and R ³¹ may be linear or branched.

In the compound represented by formula (C1), when Y ⁵ is an oxygen atom, the number of carbon atoms of the alkyl group represented by R ³⁰ is preferably 1 to 20 in order to allow rapid modification. Moreover, the number of carbon atoms of the alkyl group represented by R ³⁰ is more preferably 1 to 3, and still more preferably 1.

In the compound represented by formula (C1), when Y ⁵ is a single bond or a sulfur atom, the number of carbon atoms of the alkyl group represented by R ³⁰ is preferably 5 to 20, more preferably 8 to 20.

In the compound represented by the formula (C1), Y ⁵ is preferably an oxygen atom in terms of rapid modification.

In the compound represented by formula (C2), it is preferable that the number of carbon atoms of the alkyl group represented by R ³⁰ and R ³² is 1 to 20, respectively, in order to facilitate rapid modification. Moreover, the number of carbon atoms of the alkyl group represented by R ³⁰ and R ³² is each independently more preferably 1 to 3, and still more preferably 1.

The number of carbon atoms of the alkyl group represented by R ³¹ in the compound represented by formula (C1) and the compound represented by formula (C2) is preferably 1 to 5, more preferably 1 to 2, and even more preferably 1 .

Specific examples of the alkyl group represented by R ³⁰ , R ³¹ and R ³² include the alkyl groups exemplified among the groups represented by R ⁶ to R ⁹ .

The number of carbon atoms of the cycloalkyl group represented by R ³⁰ , R ³¹ and R ³² is preferably 3 to 20, more preferably 3 to 11. The number of carbon atoms includes the number of carbon atoms of the substituent.

When the hydrogen atoms present in the cycloalkyl group represented by R ³⁰ , R ³¹ and R ³² are each independently substituted with an alkyl group, the number of carbon atoms in the cycloalkyl group is 4 or more. The number of carbon atoms in the alkyl group that may be substituted for the hydrogen atoms present in the cycloalkyl group is 1 to 27.

Specific examples of the cycloalkyl group represented by R ³⁰ , R ³¹ and R ³² include the cycloalkyl groups exemplified among the groups represented by R ⁶ to R ⁹ .

The unsaturated hydrocarbon groups represented by R ³⁰ , R ³¹ and R ³² may be linear, branched or cyclic.

The number of carbon atoms of the unsaturated hydrocarbon group represented by R ³⁰ , R ³¹ and R ³² is preferably 5 to 20, more preferably 8 to 20.

The unsaturated hydrocarbon group represented by R ³⁰ , R ³¹ and R ³² is preferably an alkenyl group, more preferably an alkenyl group having 8 to 20 carbon atoms.

Examples of the alkenyl group represented by R ³⁰ , R ³¹ and R ³² include a single bond between any one of the carbon atoms in the linear or branched alkyl group represented by R ⁶ to R ⁹ ( CC) is replaced by a double bond (C=C). In alkenyl groups, the position of the double bond is not limited.

Preferred examples of such alkenyl groups include vinyl, propenyl, 3-butenyl, 2-butenyl, 2-pentenyl, 2-hexenyl, 2-nonenyl, 2-dodecenyl, 9-octadecenyl.

R ³⁰ and R ³² are preferably an alkyl group or an unsaturated hydrocarbon group, more preferably an alkyl group.

R ³¹ is preferably a hydrogen atom, an alkyl group or an unsaturated hydrocarbon group, more preferably an alkyl group.

If the alkyl group, cycloalkyl group and unsaturated hydrocarbon group represented by R ³¹ has the above number of carbon atoms, the compound represented by formula (C1) and the compound represented by formula (C2) are easily hydrolyzed and a modified form is easily generated. Therefore, the modified form of the compound represented by formula (C1) and the modified form of the compound represented by formula (C2) can easily cover the surface of (1) the semiconductor material. As a result, it is considered that (1) the semiconductor material is less likely to deteriorate even in a thermal environment and that a (1) semiconductor material with high durability can be obtained.

Specific examples of the compound represented by formula (C1) include: tetraethoxysilane, tetramethoxysilane, tetrabutoxysilane, tetrapropoxysilane, tetraisopropoxysilane, 3- Aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, trimethoxyphenylsilane, ethoxytriethylsilane, methoxytrimethylsilane, methoxydimethylsilane (Phenyl)silane, pentafluorophenylethoxydimethylsilane, trimethylethoxysilane, 3-chloropropyldimethoxymethylsilane, (3-chloropropyl)diethoxy (Methyl)silane, (chloromethyl)dimethoxy(methyl)silane, (chloromethyl)diethoxy(methyl)silane, diethoxydimethylsilane, dimethoxydimethylsilane Methylsilane, dimethoxydiphenylsilane, dimethoxymethylphenylsilane, diethoxydiphenylsilane, dimethoxymethylvinylsilane, diethoxy(methyl) Phenylsilane, dimethoxy(methyl)(3,3,3-trifluoropropyl)silane, allyltriethoxysilane, allyltrimethoxysilane, (3-bromopropyl) Trimethoxysilane, cyclohexyltrimethoxysilane, (chloromethyl)triethoxysilane, (chloromethyl)trimethoxysilane, dodecyltriethoxysilane, dodecyltrimethoxysilane Silane, triethoxyethylsilane, decyltrimethoxysilane, ethyltrimethoxysilane, hexyltriethoxysilane, hexyltrimethoxysilane, hexadecyltrimethoxysilane, trimethoxy( Methyl)silane, triethoxymethylsilane, trimethoxy(1H,1H,2H,2H-heptadecafluorodecyl)silane, triethoxy-1H,1H,2H,2H-tridedecafluorodecyl Octylsilane, trimethoxy(1H,1H,2H,2H-nonafluorohexyl)silane, trimethoxy(3,3,3-trifluoropropyl)silane, 1H,1H,2H,2H-perfluorooctyl Triethoxysilane, etc.

Among them, as the compound represented by formula (C1), preferred are trimethoxyphenylsilane, methoxydimethyl(phenyl)silane, dimethoxydiphenylsilane, and dimethoxymethylbenzene Silane, cyclohexyltrimethoxysilane, dodecyltriethoxysilane, dodecyltrimethoxysilane, decyltrimethoxysilane, hexyltriethoxysilane, hexyltrimethoxysilane, Hexalkyltrimethoxysilane, trimethoxy(1H,1H,2H,2H-heptadecafluorodecyl)silane, triethoxy-1H,1H,2H,2H-tridecafluoro-n-octylsilane, trimethyl Oxy(1H,1H,2H,2H-nonafluorohexyl)silane, trimethoxy(3,3,3-trifluoropropyl)silane, 1H,1H,2H,2H-perfluorooctyltriethoxy Silane, tetraethoxysilane, tetramethoxysilane, tetrabutoxysilane, tetraisopropoxysilane, more preferably tetraethoxysilane, tetramethoxysilane, tetrabutoxysilane, tetraisopropoxysilane Propoxysilane, preferably tetramethoxysilane.

Furthermore, as the compound represented by formula (C1), dodecyltrimethoxysilane, trimethoxyphenylsilane, 1H, 1H, 2H, 2H-perfluorooctyltriethoxysilane, trimethyl Oxy(1H,1H,2H,2H-nonafluorohexyl)silane.

(3. Compounds represented by formula (A5-51), compounds represented by formula (A5-52)) As the modified group (5), compounds represented by the following formula (A5-51) and compounds represented by the following formula (A5-52) may also be used.

[Chemical 11]

In formula (A5-51) and formula (A5-52), A ^C is a divalent hydrocarbon group, and Y ¹⁵ is an oxygen atom or a sulfur atom.

In formula (A5-51) and formula (A5-52), R ¹²² and R ¹²³ each independently represent a hydrogen atom, an alkyl group or a cycloalkyl group.

In formula (A5-51) and formula (A5-52), R ¹²⁴ represents an alkyl group or a cycloalkyl group.

In formula (A5-51) and formula (A5-52), R ¹²⁵ and R ¹²⁶ each independently represent a hydrogen atom, an alkyl group, an alkoxy group or a cycloalkyl group.

When R ¹²² to R ¹²⁶ are alkyl groups, they may be linear or branched. The number of carbon atoms of the alkyl group is usually 1 to 20, preferably 5 to 20, more preferably 8 to 20.

When R ¹²² to R ¹²⁶ are cycloalkyl groups, the cycloalkyl group may have an alkyl group as a substituent. 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.

The hydrogen atoms contained in the alkyl group and cycloalkyl group represented by R ¹²² to R ¹²⁶ may be independently substituted with a halogen atom or an amino group.

Examples of the halogen atom that can substitute for the hydrogen atom contained in the alkyl group or cycloalkyl group represented by R ¹²² to R ¹²⁶ include: fluorine atom, chlorine atom, bromine atom, and iodine atom. From the viewpoint of chemical stability Preferably it is a fluorine atom.

Specific examples of the alkyl group for R ¹²² to R ¹²⁶ include the alkyl groups exemplified for R ⁶ to R ⁹ .

Specific examples of the cycloalkyl group of R ¹²² to R ¹²⁶ include the cycloalkyl groups exemplified for R ⁶ to R ⁹ .

Examples of the alkoxy group of R ¹²⁵ and R ¹²⁶ include a monovalent group in which the linear or branched alkyl group exemplified for R ⁶ to R ⁹ and an oxygen atom are bonded.

When R ¹²⁵ and R ¹²⁶ are alkoxy groups, examples thereof include methoxy, ethoxy, butoxy, etc., and methoxy is preferred.

The divalent hydrocarbon group represented by A ^C only needs to be a group obtained by removing two hydrogen atoms from a hydrocarbon compound. The hydrocarbon compound may be an aliphatic hydrocarbon, an aromatic hydrocarbon, or a saturated aliphatic hydrocarbon. When A ^C is an alkylene group, it may be linear or branched. The number of carbon atoms of the alkylene group is usually 1 to 100, preferably 1 to 20, more preferably 1 to 5.

As the compound represented by formula (A5-51), preferred are trimethoxy[3-(methylamino)propyl]silane, 3-aminopropyltriethoxysilane, and 3-aminopropyl Dimethoxymethylsilane, 3-aminopropyldiethoxymethylsilane, 3-aminopropyltrimethoxysilane.

As the compound represented by formula (A5-51), a compound in which R ¹²² and R ¹²³ are hydrogen atoms, R ¹²⁴ is an alkyl group, and R ¹²⁵ and R ¹²⁶ are an alkoxy group is preferred. For example, 3-aminopropyltriethoxysilane and 3-aminopropyltrimethoxysilane are more preferred.

As the compound represented by formula (A5-51), 3-aminopropyltrimethoxysilane is more preferred. As the compound represented by formula (A5-52), 3-mercaptopropyltrimethoxysilane and 3-mercaptopropyltriethoxysilane are more preferred.

(Sodium silicate) As the modifier group (5), sodium silicate (Na ₂ SiO ₃ ) may be used.

Sodium silicate can be hydrolyzed and modified by treatment with an acid.

In this embodiment, only one type of the above-mentioned (5) modified body group may be used, or two or more types may be used in combination.

＜About the mixing ratio of each ingredient＞ In the composition of this embodiment, the compounding ratio of (1) the semiconductor material and (2) the surface modification agent can be appropriately determined depending on the types of components constituting the composition. In the composition of this embodiment, the molar ratio of (1) semiconductor material and (2) surface modification agent [(1) semiconductor material/(2) surface modification agent] may be 0.0001 to 1000, or may be 0.01 to 100. A resin composition with a relative range of the blending ratio of (1) the semiconductor material and (2) the surface modifier is within the above range is preferred in that (1) the semiconductor material is less likely to agglomerate and can exhibit good luminescence properties. .

In the composition of this embodiment, when (1) the semiconductor material is a perovskite compound, the molar ratio of the metal ion as the B component of the perovskite compound to (2) the N element of the tertiary amine [ N/B] can be 0.001~100, 0.01~10, or 0.1~1.

In the composition of this embodiment, the blending ratio of (1) the semiconductor material and (5) the modifier group may be such that the durability-improving effect of the (5) modifier group can be exerted. It can be appropriately determined based on (1) the type of semiconductor material and (5) the modifier group. In the composition of this embodiment, when (1) the semiconductor material is a perovskite compound, the metal ions as the B component of the semiconductor material and (5) the mole of the Si element of the modifier group are The ratio [Si/B] may be 0.001 to 2000 or 0.01 to 500.

In the composition of this embodiment, (5) the modified group is a silazane represented by formula (B1) or (B2) and its modified form, and (1) the semiconductor material is a perovskite compound In this case, the molar ratio [Si/B] of (1) metal ions as the B component of the semiconductor material and (5) Si of the modifier group may be 1 to 1000, 10 to 500, or 20 ~300.

In the composition of this embodiment, when (5) the modifier group is polysilazane having a structure represented by formula (B3), and (1) the semiconductor material is a perovskite compound, (1) ) The molar ratio [Si/B] of the metal ions of the B component of the semiconductor material and the Si element of the (5) modifier group may be 0.001 to 2000, or 0.01 to 2000, or 0.1 to 1000, or It can be between 1 and 500, or between 2 and 300.

The correlation range of the blending ratio of (1) the semiconductor material and (5) the modifier group is such that the durability-improving effect of the (5) modifier group can be particularly well exerted by the composition within the above range. Better.

The molar ratio [Si/B] of the metal ion as the B component of the perovskite compound and the Si element of the modified body [Si/B] can be determined by the following method.

The mass (B) (unit: mol) of the metal ion as the B component of the perovskite compound is measured by inductively coupled plasma mass spectrometry (ICP-MS), and the measured value is converted Find it based on the mass of the finished product.

The material mass (Si) of the Si element of the modified body is calculated by converting the mass of the raw material compound of the modified body into a material mass and the amount of Si (material mass) contained in the raw material compound per unit mass. out. The unit mass of the raw material compound is the molecular weight of the raw material compound if the raw material compound is a low molecular compound, and the molecular weight of the repeating unit of the raw material compound if the raw material compound is a high molecular compound.

The molar ratio [Si/B] can be calculated from the mass of Si element (Si) and the mass of metal ions (B) which is the B component of the perovskite compound.

＜Production method of composition＞ Hereinafter, embodiments will be disclosed and explained about the method for producing the composition of the present invention. In addition, the composition of this embodiment is not limited to what can be produced by the manufacturing method of the composition of this embodiment below.

＜(1) Manufacturing method of semiconductor material＞ (Methods for manufacturing semiconductor materials of (i) to (vii)) The semiconductor materials of (i) to (vii) can be produced by heating a mixture of a single substance of an element constituting the semiconductor material or a compound of an element constituting the semiconductor material, and a fat-soluble solvent.

Examples of compounds containing elements constituting semiconductor materials are not particularly limited, and examples include oxides, acetates, organic metal compounds, halides, nitrates, and the like.

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

Examples of the unsaturated aliphatic hydrocarbon group having 4 to 20 carbon atoms include an oil group.

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

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

As the hydrocarbon group having 4 to 20 carbon atoms, a saturated aliphatic hydrocarbon group and an unsaturated aliphatic hydrocarbon group are preferred.

Examples of nitrogen-containing compounds include amines and amides. Examples of oxygen-containing compounds include fatty acids.

Among such fat-soluble solvents, nitrogen-containing compounds having a hydrocarbon group having 4 to 20 carbon atoms are preferred. Preferred examples of such nitrogen-containing compounds include n-butylamine, isobutylamine, n-pentylamine, n-hexylamine, octylamine, decylamine, dodecylamine, and hexadecylamine. Alkyl amines such as octadecylamine, or alkenyl amines such as oleylamine.

Such lipophilic solvents can bond to the surface of semiconductor materials produced by synthesis. Examples of bonds when the fat-soluble solvent is bonded to the surface of the semiconductor material include chemical bonds such as covalent bonds, ionic bonds, coordination bonds, hydrogen bonds, and Van der Waals bonds.

The heating temperature of the above-mentioned mixed liquid can be appropriately set according to the type of raw material (single substance or compound) used. The heating temperature of the mixed liquid is, for example, preferably 130 to 300°C, more preferably 240 to 300°C. It is preferable that the heating temperature is equal to or higher than the above-mentioned lower limit value because the crystal structure can be easily unified. If the heating temperature is below the above upper limit, it is preferable because the crystal structure of the produced semiconductor material is less likely to collapse and the target object can be easily obtained.

The heating time of the mixed liquid can be set appropriately according to the type of raw material (element or compound) used and the heating temperature. The heating time of the mixed liquid is preferably from several seconds to several hours, and more preferably from 1 to 60 minutes.

In the above method for manufacturing a semiconductor material, a precipitate containing the target semiconductor material is obtained by cooling the heated mixed liquid. Separate the precipitate and clean it appropriately to obtain the target semiconductor material.

A solvent in which the synthetic semiconductor material is insoluble or insoluble can also be added to the supernatant after separation of the precipitate to reduce the solubility of the semiconductor material in the supernatant to generate a precipitate, and recover the semiconductor contained in the supernatant. Material. Examples of "solvents in which semiconductor materials are insoluble or poorly soluble" include methanol, ethanol, acetone, acetonitrile, and the like.

In the above method of manufacturing a semiconductor material, the separated precipitate can also be added to an organic solvent (such as chloroform, toluene, hexane, n-butanol, etc.) to prepare a solution containing the semiconductor material.

(Method for manufacturing semiconductor materials of (viii)) The manufacturing method of the semiconductor material in (viii) can refer to existing literature (Nano Lett. 2015, 15, 3692-3696, ACSNano, 2015, 9, 4533-4542), and is manufactured by the method described below.

(First manufacturing method) Examples of a method for producing a perovskite compound include a method including the steps of dissolving a compound containing component A, a compound containing component B, and a compound containing component X constituting the perovskite compound in a first solvent. solution; and mixing the obtained solution with the second solvent.

The second solvent is a solvent whose solubility to the perovskite compound is lower than that of the first solvent. In addition, the solubility means the solubility at the temperature of the step of mixing the obtained solution and the second solvent.

Examples of the first solvent and the second solvent include at least two selected from the group of organic solvents listed as (a) to (k) above.

For example, when the step of mixing the solution and the second solvent is performed at room temperature (10°C to 30°C), examples of the first solvent include (d) alcohol and (e) glycol described above. Ether, (f) organic solvent having amide group, (k) dimethylstyrene.

In addition, when the step of mixing the solution and the second solvent is performed at room temperature (10°C to 30°C), examples of the second solvent include: (a) esters, (b) ketones described above, (c) ether, (g) organic solvent having a nitrile group, (h) organic solvent having a carbonate group, (i) halogenated hydrocarbon, (j) hydrocarbon.

Hereinafter, the first manufacturing method will be described in detail. First, a compound containing component A, a compound containing component B, and a compound containing component X are dissolved in a first solvent to obtain a solution. "Compound containing component A" may also contain component X. "Compound containing B component" may also contain X component.

Next, the obtained solution and the second solvent are mixed. The step of mixing the solution and the second solvent may be (I) adding the solution to the second solvent, or (II) adding the second solvent to the solution. In order to make the particles of the perovskite compound formed by the first production method easily dispersed in the solution, it is preferable (I) to add the solution to the second solvent.

When mixing the solution and the second solvent, it is advisable to add one dropwise to the other. Moreover, it is preferable to mix the solution and the second solvent while stirring.

In the step of mixing the solution and the second solvent, the temperatures of the solution and the second solvent are not particularly limited. In order to make the obtained perovskite compound easy to precipitate, the range of -20°C to 40°C is preferred, and the range of -5°C to 30°C is more preferred. The temperature of the solution and the temperature of the second solvent may be the same or different.

The difference in the solubility of the first solvent to the perovskite compound and the solubility of the second solvent to the perovskite compound is preferably 100 μg/100 g to 90 g/100 g of solvent, more preferably 1 mg/100 g to 100 g of solvent. 90 g/solvent 100 g.

As a combination of the first solvent and the second solvent, the following is preferred: the first solvent is an organic solvent having an amide group such as N,N-dimethylacetamide or dimethyl styrene, and the second solvent is halogenated hydrocarbon or hydrocarbon. If the first solvent and the second solvent are a combination of these solvents, for example, when the mixing step is performed at room temperature (10°C to 30°C), it is easy to compare the solubility of the first solvent to the perovskite compound with that of the second solvent. 2. The difference in solubility between the solvent and the perovskite compound is controlled within 100 μg/100 g of solvent to 90 g/100 g of solvent, so it is better.

By mixing the solution and the second solvent, the solubility of the perovskite compound in the obtained mixed solution decreases, and the perovskite compound precipitates. Thereby, a dispersion liquid containing a perovskite compound is obtained.

The obtained dispersion containing the perovskite compound is subjected to solid-liquid separation, whereby the perovskite compound can be recovered. Examples of solid-liquid separation methods include filtration, concentration by solvent evaporation, and the like. Only the perovskite compound can be recovered by performing solid-liquid separation.

Furthermore, in the above-mentioned production method, in order to make the obtained perovskite compound particles easily and stably dispersed in the dispersion liquid, it is preferable to include the above-mentioned step of adding a surface modification agent.

The step of adding the surface modification agent is preferably performed before the step of mixing the solution and the second solvent. Specifically, the surface modification agent may be added to the first solvent, the solution, or the second solvent. In addition, a surface modification agent may be added to both the first solvent and the second solvent.

Moreover, in the above-mentioned production method, it is preferable to include a step of removing coarse particles by centrifugation, filtration, etc. after the step of mixing the solution and the second solvent. The size of the coarse particles removed by the removal step is preferably 10 μm or more, more preferably 1 μm or more, and further preferably 500 nm or more.

(Second manufacturing method) Examples of a method for producing a perovskite compound include a method including the steps of dissolving a compound containing component A, a compound containing component B, and a compound containing component X constituting the perovskite compound in a high-temperature third solvent. and obtain a solution; and cool the solution.

Hereinafter, the second manufacturing method will be described in detail.

First, a compound containing component A, a compound containing component B, and a compound containing component X are dissolved in a high-temperature third solvent to obtain a solution. "Compound containing component A" may also contain component X. "Compound containing component B" may also contain component X. This step may include adding each compound to a high-temperature third solvent and dissolving it to obtain a solution. In this step, each compound may be added to the third solvent and then the temperature may be raised to obtain a solution.

Examples of the third solvent include solvents capable of dissolving the compound containing component A, the compound containing component B, and the compound containing component X that are raw materials. Specifically, examples of the third solvent include the first solvent and the second solvent described above.

The so-called "high temperature" only needs to be a solvent at a temperature at which each raw material is dissolved. For example, the temperature of the high-temperature third solvent is preferably 60 to 600°C, more preferably 80 to 400°C.

Next, the solution obtained is cooled. As the cooling temperature, -20 to 50°C is preferred, and -10 to 30°C is more preferred. The cooling rate is preferably 0.1 to 1500°C/min, more preferably 10 to 150°C/min.

By cooling the high-temperature solution, the difference in solubility caused by the temperature difference of the solution can be used to precipitate the perovskite compound. Thereby, a dispersion liquid containing a perovskite compound is obtained.

The obtained dispersion containing the perovskite compound is subjected to solid-liquid separation, whereby the perovskite compound can be recovered. As a solid-liquid separation method, the method disclosed in the 1st manufacturing method can be mentioned.

Furthermore, in the above-mentioned production method, in order to make the obtained perovskite compound particles easily and stably dispersed in the dispersion liquid, it is preferable to include the above-mentioned step of adding a surface modification agent.

The step of adding the surface modifier is preferably performed before the cooling step. Specifically, the surface modification agent may be added to the third solvent, or may be added to a solution containing at least one of a compound containing component A, a compound containing component B, and a compound containing component X.

Moreover, in the above-mentioned manufacturing method, it is preferable to include a step of removing coarse particles by centrifugation, filtration, etc. disclosed in the first manufacturing method after the cooling step.

(Third manufacturing method) An example of a method for producing a perovskite compound is a production method including the following steps: obtaining a first solution in which a compound containing component A and a compound containing component B constituting the perovskite compound are dissolved; obtaining a dissolved compound constituting the perovskite compound; A second solution of the compound containing the X component; mixing the first solution and the second solution to obtain a mixed liquid; and cooling the obtained mixed liquid.

Hereinafter, the third manufacturing method will be described in detail.

First, a compound containing component A and a compound containing component B are dissolved in a high-temperature fourth solvent to obtain a first solution.

Examples of the fourth solvent include solvents capable of dissolving the compound containing component A and the compound containing component B. Specifically, examples of the fourth solvent include the third solvent described above.

The term "high temperature" may be a temperature at which the compound containing component A and the compound containing component B are dissolved. For example, the temperature of the high-temperature fourth solvent is preferably 60 to 600°C, more preferably 80 to 400°C.

Moreover, the compound containing X component is dissolved in the 5th solvent, and the 2nd solution is obtained. The compound containing the X component may also contain the B component.

Examples of the fifth solvent include solvents capable of dissolving the compound containing the X component. Specifically, examples of the fifth solvent include the third solvent described above.

Next, the obtained first solution and second solution are mixed to obtain a mixed liquid. When mixing the first solution and the second solution, one is preferably added dropwise to the other. Moreover, it is preferable to mix the 1st solution and the 2nd solution while stirring.

Next, the obtained mixed liquid is cooled. As the cooling temperature, -20 to 50°C is preferred, and -10 to 30°C is more preferred. The cooling rate is preferably 0.1 to 1500°C/min, more preferably 10 to 150°C/min.

By cooling the mixed liquid, the perovskite compound can be precipitated by utilizing the difference in solubility caused by the temperature difference of the mixed liquid. Thereby, a dispersion liquid containing a perovskite compound is obtained.

The obtained dispersion containing the perovskite compound is subjected to solid-liquid separation, whereby the perovskite compound can be recovered. As a solid-liquid separation method, the method disclosed in the 1st manufacturing method can be mentioned.

Furthermore, in the above-mentioned production method, in order to make the obtained perovskite compound particles easily and stably dispersed in the dispersion liquid, it is preferable to include the above-mentioned step of adding a surface modification agent.

The step of adding the surface modifier is preferably performed before the cooling step. Specifically, the surface modification agent can be added to any of the fourth solvent, the fifth solvent, the first solution, the second solution, and the mixed solution.

Moreover, in the above-mentioned manufacturing method, it is preferable to include a step of removing coarse particles by centrifugation, filtration, etc. disclosed in the first manufacturing method after the cooling step.

＜＜Preparation method of composition 1＞＞ Hereinafter, in order to make the properties of the obtained composition easy to understand, the composition obtained by the composition production method 1 will be called a "liquid composition".

The liquid composition of this embodiment can be produced by mixing (1) a semiconductor material and (2) a surface modification agent with either or both of (3) a solvent and (4) a polymerizable compound.

When mixing any one or both of (1) the semiconductor material and (2) the surface modification agent and (3) the solvent and (4) the polymerizable compound, it is preferable to mix them while stirring.

When (1) the semiconductor material and (2) the surface modification agent and (4) the polymerizable compound are mixed, the temperature during mixing is not particularly limited. In order to easily mix (1) the semiconductor material and (2) the surface modification agent uniformly, the range of 0°C to 100°C is preferred, and the range of 10°C to 80°C is more preferred.

(Method for producing liquid composition containing (3) solvent) As a manufacturing method of the composition containing (1) a semiconductor material, (2) a surface modification agent, and (3) a solvent, the following manufacturing method (a1) or the following manufacturing method (a2) may be sufficient, for example.

The manufacturing method (a1) is a manufacturing method of a composition including the following steps: mixing (1) a semiconductor material and (3) a solvent; and mixing the obtained mixture with (2) a surface modification agent.

The manufacturing method (a2) is a manufacturing method of a composition including the following steps: mixing (1) a semiconductor material and (2) a surface modification agent; and mixing the obtained mixture with (3) a solvent.

The (3) solvent used in the manufacturing methods (a1) and (a2) is preferably one that is difficult to dissolve the above-mentioned (1) semiconductor material. When such a solvent (3) is used, the mixture obtained by the production method (a1) and the composition obtained by the production methods (a1) and (a2) become a dispersion liquid.

When the composition of this embodiment contains (5) the modified group, the composition may be produced by using the production method (a3) of the following (5A), or by using the following (5A). Manufacturing method (a4). (5A): Selected from silazane, a compound represented by formula (C1), a compound represented by formula (C2), a compound represented by formula (A5-51), a compound represented by formula (A5-52), and one or more compounds in the group consisting of sodium silicate

In the following description, the above-mentioned (5A) is referred to as "(5A) raw material compound". The (5) modified body group is obtained by subjecting the (5A) raw material compound to a modification treatment.

The manufacturing method (a3) is a manufacturing method of a composition including the following steps: mixing (1) a semiconductor material and (3) a solvent; and mixing the obtained mixture with (2) a surface modification agent and (5A) a raw material compound. ; and perform modification treatment on the obtained mixture.

The manufacturing method (a4) is a manufacturing method of a composition including the following steps: mixing (1) a semiconductor material, (2) a surface modification agent and (5A) a raw material compound; and mixing the obtained mixture with (3) a solvent. ; and perform modification treatment on the obtained mixture.

The polymer (4-1) can be dissolved or dispersed in the solvent (3).

In the mixing step included in the above-mentioned manufacturing method, from the viewpoint of improving dispersibility, stirring is preferred.

In the mixing step included in the above-mentioned manufacturing method, the temperature is not particularly limited. From the perspective of uniform mixing, the temperature is preferably in the range of 0°C or more and 100°C or less, and more preferably in the range of 10°C or more and 80°C or less.

From the viewpoint of improving the dispersibility of (1) the semiconductor material, the manufacturing method of the composition is preferably the manufacturing method (a1) or the manufacturing method (a3).

(implementation of modification treatment method) Examples of the modification treatment method include known methods such as a method of irradiating the (5A) raw material compound with ultraviolet rays and a method of reacting the (5A) raw material compound with water vapor. In the following description, the treatment of reacting the raw material compound (5A) with water vapor may be called "humidification treatment".

Among them, it is preferable to implement humidification treatment from the viewpoint of (1) forming a stronger protection area near the semiconductor material.

The wavelength of ultraviolet rays used in the method of irradiating ultraviolet rays is usually 10 to 400 nm, preferably 10 to 350 nm, and more preferably 100 to 180 nm. Examples of light sources that generate ultraviolet rays include metal halide lamps, high-pressure mercury lamps, low-pressure mercury lamps, xenon arc lamps, carbon arc lamps, excimer lamps, and UV laser light.

When performing humidification treatment, for example, the composition may be allowed to stand for a period of time under the temperature and humidity conditions described below, or may be stirred.

The temperature during the humidification treatment only needs to be a temperature at which modification can be sufficiently carried out. The temperature in the humidification treatment is, for example, preferably 5 to 150°C, more preferably 10 to 100°C, further preferably 15 to 80°C.

The humidity in the humidification treatment only needs to be a humidity that supplies sufficient moisture to the (5A) raw material compound in the composition. The humidity in the humidification treatment is, for example, preferably 30% to 100%, more preferably 40% to 95%, and further preferably 60% to 90%. The above-mentioned humidity means the relative humidity at the temperature at which humidification treatment is performed.

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

From the viewpoint of improving the dispersibility of the raw material compound (5A) contained in the composition, stirring is preferred.

The water in the humidification process can be supplied by passing a gas containing water vapor into the reaction container, or by stirring in an atmosphere containing water vapor to supply water from the interface.

When gas containing water vapor is introduced into the reaction vessel, in order to improve the durability of the composition obtained, the flow rate of the gas containing water vapor is preferably 0.01 L/min or more and 100 L/min or less, more preferably 0.1 L/min or more and 10 L/min or less, and more preferably 0.15 L/min or more and 5 L/min or less. Examples of the gas containing water vapor include nitrogen gas containing a saturated amount of water vapor.

When (1) the semiconductor material is a perovskite compound, in the method for producing the composition of this embodiment, (2) the surface modifier, (3) the solvent, and (5) the modifier group may be in the above ( 1) The manufacturing method of semiconductor materials includes mixing in any step. For example, the following manufacturing method (a5) may be used, or the following manufacturing method (a6) may be used.

Examples of the production method (a5) include a production method including the following steps: a compound containing component B, a compound containing component X, and a compound containing component A, (2) a surface modification agent, and (5) The modified group is dissolved in the first solvent to obtain a solution; and the obtained solution is mixed with the second solvent. The first solvent and the second solvent are the same as the above solvents.

Examples of the production method (a6) include a production method including the following steps: a compound containing component B, a compound containing component X, and a compound containing component A, (2) a surface modification agent, and (5) The modified group is dissolved in a high-temperature third solvent to obtain a solution; and the solution is cooled. The third solvent is the same as the above solvent.

The conditions of each step included in these manufacturing methods are the same as the conditions in the first manufacturing method and the second manufacturing method in the manufacturing method of semiconductor material described in (viii) above.

(Method for producing liquid composition containing (4) polymerizable compound) Examples of methods for producing a composition containing (1) a semiconductor material, (2) a surface modification agent, (4) a polymerizable compound, and (5) a modified group include the following production methods (c1) to (c3) .

The manufacturing method (c1) is a manufacturing method including the following steps: dispersing (1) a semiconductor material in (4) a polymerizable compound to obtain a dispersion; and combining the obtained dispersion with (2) a surface modification agent and (5) The modified body groups are mixed.

The manufacturing method (c2) is a manufacturing method including the following steps: dispersing (2) a surface modifier and (5) a modifier group in (4) a polymerizable compound to obtain a dispersion; and combining the obtained dispersion with ( 1) Semiconductor materials are mixed.

The manufacturing method (c3) is a manufacturing method including the steps of dispersing a mixture of (1) a semiconductor material, (2) a surface modifier, and (5) a modifier group in (4) a polymerizable compound.

Among the manufacturing methods (c1) to (c3), the manufacturing method (c1) is preferred from the viewpoint of improving (1) the dispersibility of the semiconductor material.

In the manufacturing methods (c1) to (c3), in the step of obtaining each dispersion, the (4) polymerizable compound may be added dropwise to each material, or each material may be added dropwise to the (4) polymerizable compound. middle. In order to facilitate uniform dispersion, it is preferred to dropwise add at least one of (1) a semiconductor material, (2) a surface modifier, and (5) a modifier group into (4) a polymerizable compound.

In the manufacturing methods (c1) to (c3), in each mixing step, the dispersion may be added dropwise to each material, or each material may be added dropwise to the dispersion. In order to facilitate uniform dispersion, at least one of (1) the semiconductor material, (2) the surface modifier, and (5) the modifier group is preferably added dropwise to the dispersion.

At least one of the solvent (3) and the polymer (4-1) can be dissolved or dispersed in the polymerizable compound (4).

The solvent for dissolving or dispersing the polymer (4-1) is not particularly limited. The solvent is preferably one that does not easily dissolve (1) the semiconductor material. Examples of the solvent that dissolves the polymer (4-1) include the same solvents as the third solvent described above.

Among them, the second solvent has lower polarity and is less likely to dissolve (1) the semiconductor material, so it is preferable.

Among the second solvents, halogenated hydrocarbons and hydrocarbons are more preferred.

Moreover, the manufacturing method of the composition of this embodiment may be the following manufacturing method (c4), or may be manufacturing method (c5).

The manufacturing method (c4) is a manufacturing method of a composition including the following steps: (1) a semiconductor material is dispersed in (3) a solvent to obtain a dispersion; and (4) a polymerizable compound is mixed in the obtained dispersion to obtain a mixture. liquid; and mix the obtained mixed liquid with (2) surface modifier and (5) modified body group.

The manufacturing method (c5) is a manufacturing method of a composition including the following steps: dispersing (1) a semiconductor material in (3) a solvent to obtain a dispersion; and combining the obtained dispersion with (2) a surface modification agent and (5A) The raw material compounds are mixed to obtain a mixed liquid; the obtained mixed liquid is modified to obtain a mixed liquid containing (5) the modified group; and the obtained mixed liquid is mixed with (3) the polymerizable compound.

In the production method 1 of the composition, when using (6) other surface modifiers, they can be added together with the (2) surface modifiers.

＜＜Production method of composition 2＞＞ Examples of a method for producing the composition of the present embodiment include a method including the following steps: mixing (1) a semiconductor material, (2) a surface modifier, (4) a polymerizable compound, and (5) a modified body group. ; and polymerize (4) the polymerizable compound.

In the composition obtained by the composition production method 2, (1) semiconductor material, (2) surface modifier, (4-1) polymer, (5) modified body relative to the total mass of the composition The total of the groups is preferably 90% by mass or more.

In addition, as a method for producing the composition of this embodiment, a method including (4-1) polymerization of (1) a semiconductor material, (2) a surface modification agent, and (3) a solvent can also be cited. The substances and (5) modified groups are mixed; and (3) the solvent is removed.

The mixing step included in the above-mentioned manufacturing method can adopt the same mixing method as disclosed in the manufacturing method 1 of the composition described above.

Examples of methods for producing the composition include the following methods (d1) to (d6).

The manufacturing method (d1) is a manufacturing method including the following steps: (1) a semiconductor material is dispersed in (4) a polymerizable compound to obtain a dispersion; the obtained dispersion is mixed with (2) a surface modifier and (5) a modification agent. The plastid group is mixed; and (4) the polymerizable compound is polymerized.

The manufacturing method (d2) is a manufacturing method including the following steps: dispersing (1) a semiconductor material in (3) a solvent in which a polymer (4-1) is dissolved to obtain a dispersion; and combining the obtained dispersion with (2) The surface modifier and (5) modifier group are mixed; and the solvent is removed.

The manufacturing method (d3) is a manufacturing method including the following steps: dispersing (2) a surface modifier and (5) a modifier group in (4) a polymerizable compound to obtain a dispersion; and combining the obtained dispersion with ( 1) mixing the semiconductor material; and polymerizing (4) the polymerizable compound.

The manufacturing method (d4) is a manufacturing method including the following steps: dispersing (2) a surface modifier and (5) a modifier group in (3) a solvent in which (4-1) polymer is dissolved to obtain a dispersion; The obtained dispersion is mixed with (1) the semiconductor material; and the solvent is removed.

The manufacturing method (d5) is a manufacturing method including the following steps: dispersing a mixture of (1) a semiconductor material, (2) a surface modifier, and (5) a modifier group in (4) a polymerizable compound; and (4) The polymerizable compound polymerizes.

The manufacturing method (d6) is a manufacturing method including the following steps: dispersing a mixture of (1) a semiconductor material, (2) a surface modifier, and (5) a modifier group in (3) in which (4-1) polymer is dissolved ) solvent; and removing the solvent.

The step of removing the solvent (3) included in the manufacturing methods (d2), (d4) and (d6) can be a step of letting it stand at room temperature to dry naturally, or it can also be drying under reduced pressure using a vacuum dryer. It may also be a step of evaporating (3) the solvent by heating.

Regarding the step of removing (3) the solvent, for example, the solvent (3) can be removed by drying at a temperature of 0° C. or more and 300° C. or less for 1 minute or more and 7 days or less.

The step of polymerizing the polymerizable compound (4) included in the production methods (d1), (d3) and (d5) can be performed by appropriately utilizing a known polymerization reaction such as radical polymerization.

For example, in the case of free radical polymerization, a free radical polymerization initiator is added to a mixture of (1) semiconductor material, (2) surface modification agent, (4) polymerizable compound, and (5) modifier group to generate free radical polymerization. group, thereby initiating the polymerization reaction.

The radical polymerization initiator is not particularly limited, and examples thereof include photo radical polymerization initiators.

Examples of the photoradical polymerization initiator include bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide.

In the production method 2 of the composition, when using (6) other surface modifiers, they can be added together with the (2) surface modifiers.

＜＜Production method of composition 3＞＞ Moreover, the manufacturing method of the composition of this embodiment can also adopt the manufacturing method of the following (d7).

The manufacturing method (d7) is a manufacturing method including the following steps: melting and kneading (1) semiconductor material, (2) surface modification agent and (4-1) polymer.

The manufacturing method (d8) is a manufacturing method including the following steps: melting and kneading (1) semiconductor material, (2) surface modification agent, (4-1) polymer and (5A) raw material compound; and (4-1) ) Modification treatment is carried out while the polymer is in a molten state.

The manufacturing method (d9) is a manufacturing method including the following steps: manufacturing a liquid composition containing (1) a semiconductor material and (2) a surface modification agent; extracting a solid component from the obtained liquid composition; and The obtained solid component is melt-kneaded with the polymer (4-1).

The manufacturing method (d10) is a manufacturing method including the following steps: manufacturing a liquid composition containing (1) a semiconductor material, (2) a surface modification agent, and (5) a modifier group; Extract the solid content; and melt and knead the obtained solid content with the polymer (4-1).

The manufacturing method (d11) is a manufacturing method including the following steps: manufacturing a liquid composition containing (1) a semiconductor material and (2) a surface modification agent; extracting a solid component from the obtained liquid composition; and The obtained solid component, (5) modified body group and (4-1) polymer are melted and kneaded.

In the melting and kneading steps of the manufacturing methods (d7) to (d11), the mixture of the (4-1) polymer and other materials can be melted and kneaded, and other materials can also be added to the molten (4-1) polymer. . The so-called "other materials" refer to materials used in various manufacturing methods other than (4-1) polymers, specifically (1) semiconductor materials, (2) surface modifiers, (5A) raw material compounds and (5) modifications. Plastid group.

The (5) modified body group added in the melting and kneading step of the manufacturing method (d11) is obtained by modifying the (5A) raw material compound.

As a method of melt-kneading the polymer (4-1) in the production methods (d7) to (d11), a method known as a kneading method of polymers can be used. For example, extrusion processing using a single-screw extruder or a twin-screw extruder can be used.

The method described above can be used in the step of performing the modification treatment in the manufacturing method (d8).

The step of manufacturing the liquid composition in the manufacturing methods (d9) and (d11) can adopt the manufacturing method (a1) or (a2) described above.

The step of manufacturing the liquid composition in the manufacturing method (d10) can adopt the manufacturing method (a3) or (a4) described above.

The step of extracting the solid content of the manufacturing methods (d9) to (d11) can be accomplished by removing (3) the solvent constituting the liquid composition from the liquid composition by using methods such as heating, reduced pressure, air blowing, and combinations thereof. (4) polymerizable compound.

In the composition manufacturing method 3, when using (6) other surface modifiers, they can be added together with the (2) surface modifiers.

≪Measurement of perovskite compounds≫ The amount of the perovskite compound contained in the composition of this embodiment can be determined by using an inductively coupled plasma mass spectrometer ICP-MS (for example, ELAN DRCII manufactured by PerkinElmer) and an ion chromatograph (such as Thermo Fisher Scientific, Inc. Integrion) was measured. Use a good solvent such as N,N-dimethylformamide to dissolve the perovskite compound and perform the measurement. ≪(5)Measurement of the concentration of Si element contained in the modified body group≫ The concentration (μg/g) of the Si element contained in (5) the modifier group contained in the composition of this embodiment is measured using an inductively coupled plasma mass spectrometer ICP-MS (for example, ELAN DRCII manufactured by PerkinElmer). . Each measurement is performed using a solution of a good solvent such as N,N-dimethylformamide and the modified group (5).

≪Measurement of Emission Spectrum≫ The emission spectrum of the composition of this embodiment was measured using an absolute PL quantum yield measuring device (for example, C9920-02 manufactured by Hamamatsu Photonics Co., Ltd.) with excitation light of 450 nm, room temperature, and atmosphere.

≪Measurement of quantum yield≫ The quantum yield of the composition of this embodiment is measured using an absolute PL quantum yield measuring device (for example, C9920-02 manufactured by Hamamatsu Photonics Co., Ltd.) with excitation light of 450 nm, room temperature, and atmosphere.

≪Evaluation of heat resistance≫ The composition of this embodiment was heated on a hot plate at 260° C. for 2 minutes, the quantum yield before and after heating was measured, and the maintenance rate was evaluated using the following formula. Maintenance rate (%) = quantum yield after heat resistance test ÷ quantum yield before heat resistance test × 100

In each of the above measurement methods, the maintenance rate of the composition according to the embodiment may be 20% or more, 40% or more, 60% or more, 80% or more, or 85% or more. To the extent that the effect of heat resistance of the composition is high, the maintenance rate should be high.

＜＜Film＞＞ The film of this embodiment uses the above composition as a forming material. For example, the film of this embodiment contains (1) a semiconductor material, (2) a surface modification agent, and (4-1) a polymer, and relative to the total mass of the film, (1) the semiconductor material, (2) the surface modification agent, and (4-1) The total amount of polymers is 90% by mass or more.

The shape of the film is not particularly limited and may be any shape such as sheet shape or rod shape. In this specification, the so-called "rod-like shape" means, for example, a strip-like shape extending in one direction when viewed from above. As a strip-like shape in a plan view, a plate-like shape with each side having different lengths can be exemplified.

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

In this specification, the thickness of the above-mentioned film refers to the distance between the front and back sides of the film in the thickness direction when the side with the smallest median value among the length, width, and height of the film is taken as the "thickness direction." Specifically, use a micrometer to measure the thickness of the film at any three points on the film, and take the average of the measured values at the three points as the thickness of the film.

The film can be a single layer or multiple layers. In the case of multiple layers, the same type of composition may be used for each layer, or different types of compositions may be used.

＜＜Laminated structure＞＞ The laminated structure of this embodiment has a plurality of layers, and at least one layer is the above-described film.

Among the plurality of layers included in the laminated structure, examples of layers other than the above-mentioned thin film include arbitrary layers 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 sheet shape or rod shape.

(Substrate) The substrate is not particularly limited and may be a film. The substrate is preferably translucent. A multilayer structure having a light-transmissive substrate is preferred because (1) light emitted by the semiconductor material can be easily extracted.

As a material for forming the substrate, known materials such as polymers such as polyethylene terephthalate or glass can be used. For example, in a laminated structure, the thin film described above can be provided on a substrate.

FIG. 1 is a cross-sectional view schematically showing the structure of the laminated structure of this embodiment. The first laminated structure 1 a has the film 10 of this embodiment provided between the first substrate 20 and the second substrate 21 . The film 10 is sealed by a sealing layer 22 .

One aspect of the present invention is a laminated structure 1a, which is characterized in that it has a first substrate 20, a second substrate 21, the film 10 of this embodiment between the first substrate 20 and the second substrate 21, and a seal. The sealing layer 22 is disposed on the surface of the film 10 that is not in contact with the first substrate 20 and the second substrate 21 .

(barrier layer) The layers that the laminated structure of this embodiment can have are not particularly limited, and examples thereof include barrier layers. From the viewpoint of protecting the above composition from erosion by water vapor of external gases and air in the atmosphere, a barrier layer may be included.

The barrier layer is not particularly limited, but from the viewpoint of extraction of emitted light, it is preferably transparent. As the barrier layer, known barrier layers such as polymers such as polyethylene terephthalate or glass films can be used.

(light scattering layer) There are no particular limitations on the layers that the laminated structure of the present embodiment may have, and examples thereof include a light scattering layer. From the viewpoint of effectively utilizing incident light, a light scattering layer may be included. The light scattering layer is not particularly limited, but from the viewpoint of extraction of emitted light, it is preferably transparent. As the light scattering layer, known light scattering layers such as light scattering particles such as silica particles or amplifying diffusion films can be used.

＜＜Light-emitting device＞＞ The light-emitting device of this embodiment can be obtained by combining the film or laminated structure of this embodiment and a light source. A light-emitting device is a device that irradiates light emitted from a light source onto a film or laminated structure disposed in the light emission direction of the light source, thereby causing the film or laminated structure to emit light and extracting light.

Among the plurality of layers included in the laminated structure in the light-emitting device, examples of layers other than the above-mentioned film, substrate, barrier layer, and light scattering layer include: light reflective members, brightness enhancement parts, corner prism sheets, light guide plates, and inter-element layers. Any layer such as the dielectric material layer.

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

(light source) As the light source constituting the light-emitting device of this embodiment, a light source that emits (1) light included in the absorption wavelength band of the semiconductor material is used. From the viewpoint of causing the semiconductor material in the thin film or laminated structure to emit light, a light source having a light emission wavelength of 600 nm or less is preferred. As the light source, known light sources such as light-emitting diodes (LEDs) such as blue light-emitting diodes, lasers, and EL can be used.

(Light reflective member) The layers that can be included in the laminated structure constituting the light-emitting device of this embodiment are not particularly limited, and examples thereof include light-reflecting members. A light-emitting device having a light-reflecting member can efficiently irradiate light from a light source to a thin film or a laminated structure.

The light reflective member is not particularly limited and may be a reflective film. As the reflective film, known reflective films such as reflective mirrors, reflective particle films, reflective metal films, or reflectors can be used.

(brightness enhancement part) The layers that can be included in the laminated structure constituting the light-emitting device of this embodiment are not particularly limited, and examples thereof include a brightness enhancement portion. From the viewpoint of reflecting part of the light back to the light transmission direction, a brightness enhancement part may be included.

(corner prism slices) The layers that can be included in the laminated structure constituting the light-emitting device of this embodiment are not particularly limited, and examples thereof include corner prism sheets. The corner prism sheet typically has a base material part and a corner prism part. Furthermore, depending on different adjacent components, the base material portion may be omitted.

The corner prism sheet can be bonded to the adjacent components through any suitable bonding layer (eg, adhesive layer, adhesive layer).

When the light-emitting device is used in a display described below, the corner prism sheet is composed of a plurality of corner prism units protruding toward the side opposite to the viewing side (rear side). By arranging the convex portion of the corner prism sheet toward the back side, the light passing through the corner prism sheet can be easily condensed. Furthermore, if the convex portions of the corner prism sheets are arranged toward the back side, compared with the case where the convex portions are arranged toward the viewing side, less light is reflected without being incident on the corner prism sheets, and a display with higher brightness can be obtained.

(light guide plate) The layers that can be included in the laminated structure constituting the light-emitting device of this embodiment are not particularly limited, and examples thereof include a light guide plate. As the light guide plate, for example, a light guide plate formed in a lens pattern can be used on the back side, a light guide plate formed in a corner prism shape, etc. can be used on either or both sides of the back side and the viewing side. Any suitable light guide plate can be used. So that the light from the lateral direction can be deflected to the thickness direction.

(Dielectric material layer between components) The layers that can be included in the laminated structure constituting the light-emitting device of this embodiment are not particularly limited. Examples thereof include layers containing one or more dielectric materials on the optical path between adjacent elements (layers) (dielectric material layer between elements). ).

There is no particular limitation on the medium contained in the dielectric material layer between components, including vacuum, air, gas, optical materials, adhesives, optical adhesives, glass, polymers, solids, liquids, gels, and hardened materials. , optical bonding materials, refractive index matching or refractive index mismatching materials, refractive index gradient materials, coating or anti-coating materials, spacers, silica gel, brightness enhancement materials, scattering or diffusion materials, reflection or anti-reflection materials, wavelength-selective materials, wavelength-selective anti-reflective materials, color filters, or suitable media known in the above technical fields.

Specific examples of the light-emitting device according to this embodiment include a wavelength converting material for an EL display or a liquid crystal display. Specifically, each of the following structures (E1) to (E4) can be cited.

Structure (E1): The composition of this embodiment is put into a glass tube or the like, sealed, and arranged on the blue light-emitting diode as the light source and the light guide plate along the end surface (side surface) of the light guide plate. Between them, the blue light is converted into a green or red light backlight (on-edge backlight).

Structure (E2): The composition of this embodiment is formed into sheets, sandwiched between two barrier films and sealed to form a thin film. The thin film is placed on a light guide plate and is separated from the end surface of the light guide plate. The blue light emitting diode (side) irradiates the above-mentioned sheet through the light guide plate and converts it into a green light or red light backlight (surface packaging backlight).

Structure (E3): A backlight (chip package) in which the composition of the present embodiment is dispersed in resin or the like, placed near the light-emitting part of a blue light-emitting diode, and converts the irradiated blue light into green light or red light. (On-Chip) mode backlight).

Structure (E4): The composition of this embodiment is dispersed in a resist, placed on a color filter, and converted into a backlight source that converts blue light irradiated from a light source into green light or red light.

Furthermore, as a specific example of the light-emitting device of this embodiment, the composition of this embodiment is molded, placed after a blue light-emitting diode as a light source, and the blue light is converted into green light or red light. And emit white light illumination.

＜＜Display＞＞ As shown in FIG. 2 , the display 3 of this embodiment includes a liquid crystal panel 40 and the above-mentioned light-emitting device 2 in order from the viewing side. The light-emitting device 2 includes the second multilayer structure 1 b and the light source 30 . The second laminated structure 1 b is based on the above-described first laminated structure 1 a and further includes the corner prism sheet 50 and the light guide plate 60 . The display may further be provided with any suitable other components.

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

(LCD panel) The above-mentioned liquid crystal panel typically includes a liquid crystal cell, a viewing side polarizing plate disposed on the viewing side of the liquid crystal cell, and a back side polarizing plate disposed on the back side of the liquid crystal cell. The viewing side polarizing plate and the back side polarizing plate can be arranged so that their respective absorption axes are substantially orthogonal or parallel.

(LCD unit) The liquid crystal cell has a pair of substrates and a liquid crystal layer as a display medium sandwiched between the pair of substrates. In a general configuration, a color filter and a black matrix are provided on one substrate, a switching element that controls the electro-optical properties of the liquid crystal, a scanning line that provides a gate signal to the switching element and a scanning line that controls the electro-optical properties of the liquid crystal are provided on the other substrate. The signal line of the source signal, as well as the pixel electrode and the counter electrode. The distance between the substrates (cell gap) can be controlled by spacers or the like. An alignment film, for example, including polyimide, can be disposed on the side of the substrate that is in contact with the liquid crystal layer.

(Polarizing plate) The polarizing plate typically has a polarizing element and protective layers arranged on both sides of the polarizing element. The polarizing element is typically an absorption-type polarizing element. As the polarizing element, any suitable polarizing element can be used. Examples include adsorbing dichroic substances such as iodine or dichroic dyes on hydrophilic polymer films such as polyvinyl alcohol-based films, partially formalized polyvinyl alcohol-based films, and ethylene-vinyl acetate copolymer-based partially saponified films. And formed by uniaxial stretching; polyene-based alignment films such as dehydrated polyvinyl alcohol or dehydrochloric acid-treated polyvinyl chloride. Among them, a polarizing element formed by adsorbing dichroic substances such as iodine and uniaxially stretching a polyvinyl alcohol-based film is particularly preferred because of its high polarization dichroism ratio.

＜＜Use of composition＞＞ Examples of uses of the composition of this embodiment include the following uses.

＜LED＞ The composition of this embodiment can be used, for example, as a material for the light-emitting layer of a light-emitting diode (LED).

An example of an LED containing the composition of this embodiment is as follows: the composition of this embodiment and conductive particles such as ZnS are mixed and laminated to form a film, and an n-type transmission layer is layered on one surface and The structure of the p-type transport layer on the other side is that by turning on the current, the holes in the p-type semiconductor and the electrons in the n-type semiconductor cancel the charges in the particles (1) and (2) contained in the composition of the joint surface. Let this shine.

＜Solar battery＞ The composition of this embodiment can be used as an electron transport material contained in the 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 titanium oxide dense layer, a porous aluminum oxide layer, and an active layer including the composition of the present embodiment in this order. 2. 2',7,7'-Tetra(N,N'-di-methoxyphenylamine)-9,9'-Spiro-MeOTAD and other hole transport layers and silver (Ag) electrodes of solar cells.

The dense layer of titanium oxide has the function of electron transmission, the effect of suppressing the roughness of FTO, and the function of suppressing reverse electron transfer.

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

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

＜Sensor＞ The composition of this embodiment can be used as an image detection unit (image sensor), a fingerprint detection unit, a face detection unit, a vein detection unit, and an iris detection unit for solid-state imaging devices such as X-ray imaging devices and CMOS image sensors. Photoelectric conversion element (light detection element) materials are used in the detection parts of optical biosensors such as pulse oximeters and other optical biosensors that detect specific characteristics of a part of a living body.

＜＜Thin film manufacturing method＞＞ Examples of the thin film manufacturing method include the following manufacturing methods (e1) to (e3).

The manufacturing method (e1) is a thin film manufacturing method including the following steps: applying a liquid composition to obtain a coating film; and removing (3) the solvent from the coating film.

The production method (e2) is a method for producing a film including the following steps: applying a liquid composition containing (4) a polymerizable compound to obtain a coating film; and making the obtained coating film contain the (4) polymerizable compound. Perform aggregation.

The manufacturing method (e3) is a manufacturing method of a film including the step of molding the composition obtained by the above-described manufacturing methods (d1) to (d6).

The film produced by the above-mentioned production methods (e1) and (e2) can be peeled from the production position and used.

＜＜Manufacturing method of laminated structure＞＞ Examples of the manufacturing method of the laminated structure include the following manufacturing methods (f1) to (f3).

The manufacturing method (f1) is a manufacturing method of a laminated structure including the following steps: preparing a liquid composition; applying the obtained liquid composition on a substrate; and removing (3) the solvent from the obtained coating film.

The manufacturing method (f2) is a manufacturing method of a laminated structure including the following steps: laminating a film on a substrate.

The manufacturing method (f3) is a manufacturing method of a laminated structure including the following steps: manufacturing a liquid composition containing (4) a polymerizable compound; applying the obtained liquid composition on a substrate; and making the obtained coating film The polymerizable compound contained in (4) is polymerized.

The steps of producing the liquid composition in the production methods (f1) and (f3) can adopt the production methods (c1) to (c5) described above.

The step of applying the liquid composition on the substrate in the manufacturing methods (f1) and (f3) is not particularly limited, and gravure coating, rod coating, printing, spraying, spin coating, etc. can be used. Well-known coating and coating methods such as dipping method and die coating method.

The step of removing the solvent (3) in the manufacturing method (f1) may be the same step as the step of removing the solvent (3) included in the above-mentioned manufacturing methods (d2), (d4), and (d6).

The step of polymerizing the (4) polymerizable compound in the production method (f3) may be the same as the step of polymerizing the (4) polymerizable compound in the above-mentioned production methods (d1), (d3), and (d5). Same steps.

Any adhesive can be used in the step of laminating the film on the substrate in the manufacturing method (f2).

The adhesive is not particularly limited as long as it does not dissolve (1) the semiconductor material, and a known adhesive can be used.

The method of manufacturing a laminated structure may include a step of bonding an arbitrary film to the obtained laminated structure.

Examples of arbitrary films to be bonded include reflective films and diffusion films.

Any adhesive can be used in the step of laminating the film.

The above-mentioned adhesive is not particularly limited as long as it does not dissolve (1) the semiconductor material, and a known adhesive can be used.

＜＜Manufacturing method of light-emitting device>> For example, a manufacturing method includes the following steps: arranging the above-mentioned light source, and arranging the above-mentioned film or laminated structure on the optical path of the light emitted from the light source.

In addition, the technical scope of the present invention is not limited to the above-described embodiment, and various changes can be made without departing from the gist of the present invention. [Example]

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

(Measurement of N content contained in amine compounds) X-ray photoelectron spectra (XPS) of the compositions obtained in Examples 1 to 3 (Quantera SXM, manufactured by ULVAC-PHI Co., Ltd., the AlKα ray photoelectron grazing angle is 45 degrees, the aperture diameter is set to 100 μm, and The C 1s peak of surface contaminating hydrocarbons was set to 284.6 eV and used as a reference for electrostatic compensation) and the ratio of the moles of Pb in the perovskite contained in the composition to the moles of N in the amine compound was calculated ( N/Pb(mol ratio)). The XPS measurement was performed by casting 0.05 mL of the composition containing perovskite on a 1 cm × 1 cm glass substrate and drying it.

(Measurement of concentration of perovskite compounds) The concentration of the perovskite compound in the compositions obtained in Examples 1 to 3 and Comparative Example 1 was measured by the following method.

First, (1) the semiconductor material obtained by the method described below is redispersed in accurately weighed toluene, thereby obtaining a dispersion liquid. Next, N,N-dimethylformamide is added to the obtained dispersion liquid to dissolve the perovskite compound.

Thereafter, Cs and Pb contained in the dispersion liquid were quantified using ICP-MS (ELAN DRCII, manufactured by PerkinElmer). Furthermore, the Br contained in the dispersion liquid was quantified using an ion chromatograph (Integrion, manufactured by Thermo Fisher Scientific Co., Ltd.). The mass of the perovskite compound contained in the dispersion was determined from the sum of the measured values, and the concentration of the dispersion was determined from the mass of the perovskite compound and the amount of toluene.

(Measurement of quantum yield) An absolute PL quantum yield measuring device (manufactured by Hamamatsu Photonics Co., Ltd., C9920-02) was used to measure the quantum yield of the compositions obtained in Examples 1 to 3 and Comparative Example 1 under excitation light of 450 nm, room temperature, and the atmosphere. Rate.

(Heat resistance evaluation) The compositions obtained in Examples 1 to 3 and Comparative Example 1 were heated on a hot plate at 260° C. for 2 minutes to perform a heat resistance test. The quantum yield before and after the heat resistance test was measured, and the maintenance rate was calculated using the following formula. The higher the maintenance rate calculated in this way, the higher the evaluation of heat resistance. Maintenance rate (%) = quantum yield after heat resistance test ÷ quantum yield before heat resistance test × 100

((1) Observation of semiconductor materials by transmission electron microscope) (1) Semiconductor materials were observed using a transmission electron microscope (JEM-2200FS, manufactured by JEOL Ltd.). The sample for observation is obtained by collecting (1) the semiconductor material from the composition onto a grid with a support film. The observation conditions were set to an accelerating voltage of 200 kV.

For the image of the semiconductor material taken in the electron microscope photograph obtained, the distance between the parallel lines when the image is sandwiched between two parallel lines is calculated as the Ferret diameter. Find the arithmetic mean of the Ferrit diameters of 20 semiconductor materials, and find the average Ferrit diameter.

(Calculation of the molar ratio [Si/B] between the B component of the perovskite compound and the Si element of the modified body) The mass (B) (unit: mol) of the metal ion as the B component of the perovskite compound is measured by inductively coupled plasma mass spectrometry (ICP-MS), and the measured value is converted Find it based on the mass of the finished product.

The material mass (Si) of the Si element of the modified body is calculated by converting the mass of the raw material compound of the modified body into a material mass and the amount of Si (material mass) contained in the raw material compound per unit mass. out. The unit mass of the raw material compound is the molecular weight of the raw material compound if the raw material compound is a low molecular compound, and the molecular weight of the repeating unit of the raw material compound if the raw material compound is a high molecular compound.

The molar ratio [Si/B] is calculated from the mass of Si element (Si) and the mass of metal ions (B) which is the B component of the perovskite compound.

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

Mix 0.276 g of lead bromide (PbBr ₂ ) and 20 mL of 1-octadecene as the solvent. Stir with a magnetic stirrer, and heat at 120°C for 1 hour while flowing nitrogen, then add 2 mL of oleic acid and 2.117 mL of N,N-dimethyl n-octadecylamine to prepare a lead bromide dispersion. .

After the lead bromide dispersion was heated to 130°C, 1.6 mL of the above-mentioned cesium carbonate solution was added. After the addition, the reaction vessel was immersed in ice water to cool down to room temperature to obtain a dispersion.

Next, the dispersion was centrifuged at 10,000 rpm for 5 minutes to separate the precipitate. After adding 15 mL of ethyl acetate and 5 mL of toluene to disperse, the dispersion was centrifuged again at 10,000 rpm for 5 minutes to separate the precipitate. Wash after separation. After washing three times, a precipitated perovskite compound was obtained. After the perovskite compound was dispersed in 10 mL of toluene, 0.5 mL was again divided and dispersed in 4.5 mL of toluene to obtain a dispersion containing the perovskite compound and a solvent.

The concentration of the perovskite compound measured by ICP-MS and ion chromatography was 1200 ppm (μg/g). The N/Pb molar ratio determined by XPS was 0.32.

The X-ray diffraction pattern of the compound recovered after the solvent was naturally dried was measured using an X-ray diffraction measurement device (XRD, CuKα ray, The peak originating from (hkl) = (001) is confirmed to have a three-dimensional perovskite crystal structure.

Next, 100 μL of organopolysilazane (Durazane 1500 Slow Cure, manufactured by Merck Performance Materials Co., Ltd.: 0.967 g/cm ³ ) was mixed into the above dispersion liquid. In the dispersion liquid, the molar ratio of the Si element contained in the organopolysilazane and the Pb element contained in the perovskite compound is Si/Pb=172.

The above dispersion was stirred using a stirrer at a humidity of 25°C and 80%, and the modification process was carried out for 1 day.

50 μL of the modified dispersion was cast on a glass substrate with a size of 1 cm × 1 cm. After natural drying, it was baked at 100°C for 12 hours to obtain a composition. The quantum yield before and after the heat resistance test was measured and the maintenance rate was calculated. The result was that the maintenance rate was 42.7%. The results are shown in Table 1.

[Example 2] By the same method as Example 1, a dispersion liquid containing a perovskite compound and N,N-dimethyln-octadecylamine was obtained. Next, 100 μL of organopolysilazane (Durazane 1500 Rapid Cure, manufactured by Merck Performance Materials Co., Ltd.: 0.967 g/cm ³ ) was mixed into the above dispersion liquid. In the dispersion liquid, the molar ratio of the Si element contained in the organopolysilazane and the Pb element contained in the perovskite compound is Si/Pb=50.4.

The above dispersion was stirred using a stirrer at a humidity of 25°C and 80%, and the modification process was carried out for 1 day.

50 μL of the modified dispersion was cast on a glass substrate with a size of 1 cm × 1 cm. After natural drying, it was baked at 100°C for 12 hours to obtain a composition. The quantum yield before and after the durability test was measured and the maintenance rate was calculated. The result was that the maintenance rate was 86.4%. The results are shown in Table 1.

[Example 3] The same procedure as Example 2 was performed except that the added amount of organopolysilazane (Durazane 1500 Rapid Cure, manufactured by Merck Performance Materials Co., Ltd.: 0.967 g/cm ³ ) was 300 μL. method to obtain the composition. The molar ratio between the Si element contained in the organopolysilazane and the Pb element contained in the perovskite compound in the dispersion liquid is Si/Pb=151.

50 μL of the above dispersion was cast on a glass substrate with a size of 1 cm × 1 cm. After natural drying, it was baked at 100°C for 12 hours to obtain a composition. The quantum yield before and after the heat resistance test was measured and the maintenance rate was calculated. As a result, the maintenance rate was 77.9%. The results are shown in Table 1.

[Comparative example 1] Mix 0.814 g of cesium carbonate, 40 mL of 1-octadecene as solvent, and 2.5 mL of oleic acid. The mixture was stirred with a magnetic stirrer and heated at 150° C. for 1 hour while flowing nitrogen gas to prepare a cesium carbonate solution.

Mix 0.276 g of lead bromide (PbBr ₂ ) and 20 mL of 1-octadecene as the solvent. After stirring with a magnetic stirrer and heating at a temperature of 120° C. for 1 hour while flowing nitrogen, 2 mL of oleic acid and 2 mL of oleylamine were added to prepare a lead bromide dispersion.

After the lead bromide dispersion was heated to 160°C, 1.6 mL of the above-mentioned cesium carbonate solution was added. After the addition, the reaction vessel was immersed in ice water to cool down to room temperature to obtain a dispersion.

Secondly, the dispersion was centrifuged at 10,000 rpm for 5 minutes to obtain the precipitated perovskite compound. After the perovskite compound was dispersed in 5 mL of toluene, 0.5 mL was again divided and dispersed in 4.5 mL of toluene to obtain a dispersion containing the perovskite compound and oleylamine.

The concentration of the perovskite compound measured by ICP-MS and ion chromatography was 2000 ppm (μg/g).

The X-ray diffraction pattern of the compound recovered after the solvent was naturally dried was measured using an X-ray diffraction measurement device (XRD, CuKα ray, The peak originating from (hkl) = (001) is confirmed to have a three-dimensional perovskite crystal structure.

The average Ferret diameter of perovskite compounds observed by TEM is 11 nm.

After diluting the concentration of the perovskite compound to 200 ppm (μg/g) with toluene, the quantum yield measured by the quantum yield measuring device was 30%. Next, 100 μL of organopolysilazane (Durazane 1500 Slow Cure, manufactured by Merck Performance Materials Co., Ltd.: 0.967 g/cm ³ ) was mixed into the dispersion 1 containing the perovskite compound and solvent. In the dispersion liquid, the molar ratio of the Si element contained in the organopolysilazane and the Pb element contained in the perovskite compound is Si/Pb=76.

The above dispersion was stirred using a stirrer at a humidity of 25°C and 80%, and the modification process was carried out for 1 day.

50 μL of the modified dispersion was cast on a glass substrate with a size of 1 cm × 1 cm. After natural drying, it was baked at 100°C for 12 hours to obtain a composition. The quantum yield before and after the heat resistance test was measured and the maintenance rate was calculated. The result was that the maintenance rate was 8%. The results are shown in Table 1.

[Table 1] (1) surface modifier (5) Maintenance rate Kind Adding amount [μL] [%] Example 1 CsPbBr ₃ N,N-dimethyl n-octadecylamine/oleic acid Durazane 1500 Slow Cure 100 42.7 Example 2 CsPbBr ₃ N,N-dimethyl n-octadecylamine/oleic acid Durazane 1500 Rapid Cure 100 86.4 Example 3 CsPbBr ₃ N,N-dimethyl n-octadecylamine/oleic acid Durazane 1500 Rapid Cure 300 77.9 Comparative example 1 CsPbBr ₃ Oleamine/oleic acid Durazane 1500 Slow Cure 100 8

From the above results, it was confirmed that the compositions of Examples 1 to 3 to which the present invention was applied had excellent heat resistance compared to the composition of Comparative Example 1 to which the present invention was not applied.

[Reference example 1] After the compositions described in Examples 1 to 3 are put into a glass tube or the like and sealed, the composition is placed between a blue light-emitting diode as a light source and a light guide plate, thereby producing a blue light-emitting diode. The polar body's blue light is converted into green or red light backlight.

[Reference example 2] The composition described in Examples 1 to 3 can be obtained by forming a sheet, sandwiching and sealing the composition between two barrier films to obtain a film, and disposing the film on a light guide plate. A backlight source capable of converting the blue light emitted from the blue light-emitting diode located on the end surface (side) of the light guide plate to the above-mentioned sheet through the light guide plate into green light or red light is manufactured.

[Reference Example 3] The compositions described in Examples 1 to 3 are placed near the light-emitting part of the blue light-emitting diode, thereby producing a backlight capable of converting irradiated blue light into green light or red light.

[Reference Example 4] After mixing the compositions described in Examples 1 to 3 with a resist and removing the solvent, a wavelength conversion material can be obtained. The obtained wavelength conversion material is arranged between the blue light-emitting diode as the light source and the light guide plate, or arranged behind the OLED as the light source, thereby producing a device that can convert the blue light of the light source into green light or red light. the backlight.

[Reference Example 5] The compositions described in Examples 1 to 3 are mixed with conductive particles such as ZnS to form a film, and an n-type transmission layer is layered on one area and a p-type transmission layer is layered on the other area, thereby obtaining an LED. By turning on the current, the holes in the p-type semiconductor and the electrons in the n-type semiconductor offset the charges in the perovskite compound at the junction, thereby emitting light.

[Reference Example 6] A dense titanium oxide layer is laminated on the surface of a fluorine-doped tin oxide (FTO) substrate, a porous aluminum oxide layer is laminated thereon, and the compositions described in Examples 1 to 3 are laminated thereon. After removing the solvent, a porous aluminum oxide layer is laminated thereon. 2,2',7,7'-tetrakis(N,N'-di-methoxyphenylamine)-9,9'-spiro-OMeTAD and other hole transport layers are laminated on it Silver (Ag) layer to make solar cells.

[Reference Example 7] The composition of this embodiment can be obtained by removing the solvent of the composition described in Examples 1 to 3 and molding it, and disposing it in the subsequent stage of the blue light-emitting diode, thereby manufacturing a blue light-emitting diode. The blue light irradiated by the polar body to the composition is converted into green light or red light to emit white light.

[Reference Example 8] The composition of this embodiment can be obtained by removing the solvent from the composition described in Examples 1 to 3 and molding the composition. The obtained composition is made into a part of the photoelectric conversion layer, thereby producing a photoelectric conversion element (light detection element) material included in a detection part that senses light. Photoelectric conversion element materials can be used in the image detection part (image sensor), fingerprint detection part, face detection part, vein detection part and iris detection part of solid-state imaging devices such as X-ray imaging devices and CMOS image sensors, etc. for biometric detection. Optical biosensors such as detection parts and pulse oximeter that detect specific characteristics of a body part. [Industrial availability]

According to the present invention, it is possible to provide a highly heat-resistant composition containing a luminescent semiconductor material, a film using the composition, a laminated structure using the film, and a light-emitting device and a display including the laminated structure. Therefore, the composition of the present invention, the film using the composition, the laminated structure using the film, and the light-emitting device and display including the laminated structure can be favorably used for light-emitting purposes.

1a: First laminated structure 1b: Second layered structure 2:Lighting device 3: Monitor 10:Film 20: First substrate 21:Second substrate 22:Sealing layer 30:Light source 40:LCD panel 50: Corner column slices 60:Light guide plate

FIG. 1 is a cross-sectional view showing an embodiment of the laminated structure of the present invention. FIG. 2 is a cross-sectional view showing an embodiment of the display of the present invention.

Claims (6)

A composition comprising (1) component and (2) component, (1) component: luminescent semiconductor material (2) component: tertiary amine and/or tertiary ammonium cation represented by the following formula (A5) ,

(In formula (A5), R ⁴¹ and R ⁴² each independently represent an alkyl group, a cycloalkyl group, an alkenyl group or an alkynyl group, and may each independently have a substituent. The above substituent is a hydrocarbon group, an amino group, a cyano group, or a mercapto group. or nitro group, the hydrogen atoms contained in R ⁴¹ and R ⁴² can be independently substituted with halogen atoms, and the number of carbon atoms in R ⁴¹ and R ⁴² is independently 3 or less; R ⁴³ represents an alkyl group, a cycloalkyl group, Aryl, alkenyl or alkynyl groups may have substituents. The above substituents are hydrocarbon groups, amino groups, cyano groups, mercapto groups or nitro groups. The hydrogen atoms contained in R ⁴³ may be independently substituted with halogen atoms. R ⁴³ The number of carbon atoms is 8 or more) The above (1) component is a perovskite compound with A, B and The component of the vertex, and is a univalent cation; At least one of the anions; B is a component located in the center of the hexahedron with A at the vertex and the octahedron with X at the vertex in the perovskite crystal structure, and is a metal ion), and further includes (5) Component, (5) Component: selected from the group consisting of silazane, a modified form of silazane, a compound represented by the following formula (C1), a modified form of a compound represented by the following formula (C1), and the following A compound represented by the following formula (C2), a modified form of the compound represented by the following formula (C2), a compound represented by the following formula (A5-51), a compound represented by the following formula (A5-51) A modified form of a compound represented by the following formula (A5-52), a modified form of a compound represented by the following formula (A5-52), sodium silicate and a modified form of sodium silicate More than one compound in

(In formula (C1), Y ⁵ represents a single bond, an oxygen atom or a sulfur atom; when Y ⁵ is an oxygen atom, R ³⁰ and R ³¹ independently represent a hydrogen atom and an alkane with a carbon number of 1 to 20. group, a cycloalkyl group with 3 to 30 carbon atoms, or an unsaturated hydrocarbon group with 2 to 20 carbon atoms; when Y ⁵ is a single bond or a sulfur atom, R ³⁰ represents a cycloalkyl group with 1 to 20 carbon atoms. Alkyl group, cycloalkyl group with 3 to 30 carbon atoms, or unsaturated hydrocarbon group with 2 to 20 carbon atoms. R ³¹ represents a hydrogen atom, alkyl group with 1 to 20 carbon atoms, 3 to 20 carbon atoms. 30 cycloalkyl group, or an unsaturated hydrocarbon group with 2 to 20 carbon atoms; in formula (C2), R ³⁰ , R ³¹ and R ³² respectively independently represent a hydrogen atom and an alkyl group with 1 to 20 carbon atoms. , a cycloalkyl group with 3 to 30 carbon atoms, or an unsaturated hydrocarbon group with 2 to 20 carbon atoms; in formula (C1) and formula (C2), the alkyl group represented by R ³⁰ , R ³¹ and R ³² , the hydrogen atoms contained in the cycloalkyl group and the unsaturated hydrocarbon group can be independently substituted with halogen atoms or amine groups; a is an integer from 1 to 3; when a is 2 or 3, the plurality of Y ⁵ present can be the same or different; when a is 2 or 3, the plurality of R ³⁰ that exists may be the same or different; when a is 2 or 3, the plurality of R ³² that exists may be the same or different; when a is 1 or 2 , the plural R ^31s that exist may be the same or different)

(In formula (A5-51) and formula (A5-52), A ^C is a divalent hydrocarbon group, Y ¹⁵ is an oxygen atom or a sulfur atom; R ¹²² and R ¹²³ respectively independently represent a hydrogen atom and a carbon number of 1 to 20 an alkyl group, or a cycloalkyl group with 3 to 30 carbon atoms, R ¹²⁴ represents an alkyl group with 1 to 20 carbon atoms, or a cycloalkyl group with 3 to 30 carbon atoms, and R ¹²⁵ and R ¹²⁶ represent independently Hydrogen atom, alkyl group with 1 to 20 carbon atoms, alkoxy group with 1 to 20 carbon atoms, or cycloalkyl group with 3 to 30 carbon atoms; alkyl and cycloalkyl groups represented by R ¹²² to R ¹²⁶ The hydrogen atoms contained can be independently substituted with halogen atoms or amine groups). The composition of claim 1, further comprising a component selected from (3) component, (4) component and (4-1) component At least one of the group consisting of (3) component: solvent (4) component: polymeric compound (4-1) component: polymer. A film using the composition of claim 1 or 2 as a forming material. A laminated structure including the film of claim 3. A light-emitting device provided with the laminated structure of claim 4. A display having the layered structure of claim 4.