WO2020085362A1

WO2020085362A1 - Composition, film, laminate structure, light-emitting device, and display

Info

Publication number: WO2020085362A1
Application number: PCT/JP2019/041472
Authority: WO
Inventors: 翔太内藤; 謙太朗間瀬
Original assignee: 住友化学株式会社
Priority date: 2018-10-26
Filing date: 2019-10-23
Publication date: 2020-04-30
Also published as: CN112912341B; JP7133437B2; JP2020066568A; TW202028423A; TWI830795B; CN112912341A

Abstract

This composition contains a component (1) and a component (2). Component (1): a light-emitting semiconductor material Component (2): 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

Composition, film, laminated structure, light emitting device and display

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

LED backlights have been developed that include a blue LED (light emitting diode) and a composition having a light emitting property. In recent years, as a compound having a light emitting property contained in the composition, interest in a light emitting semiconductor material has been increasing (Non-Patent Document 1).

However, when a composition containing a light emitting semiconductor material as described in Non-Patent Document 1 is used as a light emitting material, further improvement in heat resistance is required.

The present invention has been made in view of the above circumstances, and is a composition having high heat resistance including a light emitting semiconductor material, a film using the composition, a laminated structure using the film, and the laminated structure. An object of the present invention is to provide a light emitting device having a body and a display.

In order to solve the above-mentioned subject, the present invention has the following modes.
[1] A composition containing the component (1) and the component (2).
(1) Component: Luminescent semiconductor material (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 a hexahedron centered on B in the perovskite type crystal structure, and is a monovalent cation.
X represents a component located at each vertex of the octahedron centered on B in the perovskite type crystal structure, and is at least one anion selected from the group consisting of a halide ion and a thiocyanate ion.
In the perovskite type crystal structure, B is a component located at the center of the hexahedron having A at its apex and the octahedron having X at its apex, and is a metal ion. )
[3] The composition according to [1] or [2], which further contains the component (5).
Component (5): silazane, silazane modified product, compound represented by the following formula (C1), modified product of compound represented by the following formula (C1), compound represented by the following formula (C2), below A modified product of the compound represented by formula (C2), a compound represented by the following formula (A5-51), a modified product of the compound represented by the following formula (A5-51), and a compound represented by the following formula (A5-52) ), One or more compounds selected from the group consisting of a compound represented by the following formula (A5-52), a modified product of sodium silicate, and a modified product of sodium silicate.

(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 are each independently 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. It represents up to 20 unsaturated hydrocarbon groups.
When Y ⁵ is a single bond or a sulfur atom, R ³⁰ is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, or an unsaturated hydrocarbon group having 2 to 20 carbon atoms. R ³¹ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, or an unsaturated hydrocarbon group having 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 a carbon atom having 3 to 30 carbon atoms. It represents 2 to 20 unsaturated hydrocarbon groups.
In formula (C1) and formula (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.
a is an integer of 1 to 3.
When a is 2 or 3, a plurality of Y ^{5 s} may be the same or different.
When a is 2 or 3, a plurality of R ^30's may be the same or different.
When a is 2 or 3, a plurality of R ^32's may be the same or different.
When a is 1 or 2, a plurality of R ^31's may be the same or different. )

(In the formulas (A5-51) and (A5-52), A ^C is a divalent hydrocarbon group, Y ¹⁵ is an oxygen atom or a sulfur atom. R ¹²² and R ¹²³ are each independently, Represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, 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 R ¹²⁵ and R ¹²⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a cycloalkyl group having 3 to 30 carbon atoms. hydrogen atoms are contained in the alkyl group and cycloalkyl group represented by .R ^{122 ~} R ¹²⁶ representing a each independently may be substituted with a halogen atom or an amino group.) [4] and (3) Min, (4) component, and (4-1) at least one selected from the group consisting of components, [1] ~ The composition according to any one of [3].
Component (3): Solvent (4) Component: Polymerizable compound (4-1) Component: 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 according to [5].
[7] A light emitting device including the laminated structure according to [6].
[8] A display including the laminated structure according to [6].

According to the present invention, there are provided a composition having high heat resistance including a light emitting semiconductor material, a film using the composition, a laminated structure using the film, a light emitting device and a display including the laminated structure. be able to.

It is sectional drawing which shows one Embodiment of the laminated structure which concerns on this invention. It is sectional drawing which shows one Embodiment of the display which concerns on this invention.

<Composition>
The light emitting semiconductor material (1) contained in the composition of the present embodiment has a light emitting property. “Luminescent” refers to the property of emitting light. The light emitting property is preferably a property of emitting light when excited by an electron, and more preferably a property of emitting light when excited by an electron 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 the present embodiment contains the component (1) and the component (2).
(1) Component: Luminescent semiconductor material (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”.

As will be described in detail later, (2) the surface modifier is a compound or ion having the action of (1) adsorbing on the surface of the semiconductor material and (1) stably dispersing the semiconductor material in the composition.

The composition of the present embodiment may be a composition containing (1) a semiconductor material and (2) a surface modifier, and may further include components other than (1) the semiconductor material and (2) the surface modifier. Good.

The composition of the present embodiment contains (1) a semiconductor material, (2) a surface modifier, and is at least selected from the group consisting of (3) component, (4) component, and (4-1) component. It may contain one kind.
(3) component: solvent (4) component: polymerizable compound (4-1) component: polymer

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

The composition of this embodiment may be dispersed in a dispersion medium.
In the present specification, “dispersed” refers to (1) a state in which a semiconductor material is suspended in a dispersion medium, or (1) a state in which a semiconductor material is suspended in a dispersion medium. (1) When the semiconductor material is dispersed in the dispersion medium, (1) part of the semiconductor material may be precipitated.

In the composition, the content ratio of the dispersion medium with respect to the total mass of the composition is not particularly limited. (1) From the viewpoint of improving the dispersibility of the semiconductor material and improving the durability, the content ratio of the dispersion medium with respect to the total mass of the composition is preferably 99.99% by mass or less, and 99.9% by mass. It is more preferably at most% by mass, further preferably at most 99% by mass.

From the viewpoint of improving durability, the content ratio of the dispersion medium to the total mass of the composition is preferably 0.1% by mass or more, more preferably 1% by mass or more, and 10% by mass or more. Is more preferred, 50% by mass or more is more preferred, 80% by mass or more is more preferred, and 90% by mass or more is most preferred.

The above upper and lower limits can be combined arbitrarily.

Examples of combinations of the upper limit value and the lower limit value are 0.1 to 99.99% by mass, 1 to 99.9% by mass, 1 to 99% by mass, 10 to 99% by mass, 20 to 99% by mass, and 50. ˜99% by mass and 90 to 99% by mass.

The composition of the present embodiment may further contain the component (5). The details of component (5) will be described later.
Component (5): silazane, silazane modified product, compound represented by the formula (C1), modified compound of the compound represented by the formula (C1), compound represented by the formula (C2), A modified product of the compound represented by the formula (C2), a compound represented by the formula (A5-51), a modified product of the compound represented by the formula (A5-51), and the formula (A5-52) ), And one or more compounds selected from the group consisting of a modified form of the compound represented by the formula (A5-52), sodium silicate, and a modified form of sodium silicate.

In the following description, the component (5) will be referred to as the "(5) modified substance group".

In the composition, the content ratio of (1) semiconductor material to the total mass of the composition is not particularly limited. From the viewpoint of making the light-emitting semiconductor material less likely to aggregate and preventing the concentration quenching, the content ratio of (1) the semiconductor material to the total mass of the composition is preferably 50 mass% or less, and 1 mass% or less. Is more preferable, and 0.3% by mass or less is further preferable. From the viewpoint of obtaining good emission intensity, the content ratio of (1) semiconductor material to the total mass of the composition is preferably 0.0001 mass% or more, and more preferably 0.0005 mass% or more. It is more preferably 0.001% by mass or more.

The above upper and lower limits can be combined arbitrarily.

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

A composition in which the content ratio of (1) semiconductor material to the total mass of the composition is within the above range is preferable because (1) aggregation of the semiconductor material is less likely to occur and luminescence is excellently exhibited.

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

The above upper and lower limits can be combined arbitrarily.

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

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

In the composition, the content ratio of the (5) modified body group to the total mass of the composition is not particularly limited. (1) From the viewpoint of improving the dispersibility of the semiconductor material and the viewpoint of improving the durability, the content ratio of the (5) modified body group to the total mass of the composition is preferably 30% by mass or less, It is more preferably 10% by mass or less, and further preferably 7.5% by mass or less. From the viewpoint of improving durability, the content ratio of (1) semiconductor material to the total mass of the composition is preferably 0.001% by mass or more, and more preferably 0.01% by mass or more. Is more preferably 0.1% by mass or more.
The upper limit value and the lower limit value can be arbitrarily combined.
Examples of the combination of the upper limit value and the lower limit value include 0.001 to 30% by mass, 0.001 to 10% by mass, and 0.1 to 7.5% by mass.
The composition in which the content ratio of the modified body group (5) to the total mass of the composition is within the above range is preferable from the viewpoint of durability.

The composition of the present embodiment may include other components other than the above (1) to (5).
The composition of the present embodiment may have, for example, the component (6). The details of the component (6) will be described later.
(6) At least one compound or ion selected from the group consisting of carboxylic acid, carboxylate ion and carboxylate salt

In the following explanation, the component (6) is referred to as “(6) other surface modifier”.

In the composition, the content ratio of (6) other surface modifier to the total mass of the composition is not particularly limited. From the viewpoint of improving durability, the content ratio of (6) the other surface modifier to the total mass of the composition is preferably 30 mass% or less, more preferably 1 mass% or less, and 0.5 It is more preferable that the content is not more than mass%. Further, (1) from the viewpoint of improving the heat resistance of the semiconductor material, it is preferably 0.0001 mass% or more, more preferably 0.001 mass% or more, and 0.01 mass% or more. Is more preferable.

The above upper and lower limits can be combined arbitrarily.

A composition in which the content ratio of (6) the other surface modifier to the total mass of the composition is within the above range is preferable because (1) the semiconductor material has excellent heat resistance.

Further, for example, the composition of the present embodiment may further contain a small amount of impurities, (1) a compound having an amorphous structure composed of elements constituting a semiconductor material, and a polymerization initiator.

In the composition of the present embodiment, the total content of some impurities, (1) the compound having an amorphous structure composed of the elements constituting the semiconductor material, and the polymerization initiator is 10% by mass or less based on the total mass of the composition. Is preferable, 5 mass% or less is more preferable, and 1 mass% or less is further preferable.

Hereinafter, (1) a semiconductor material, (2) a surface modifier, (3) a solvent, (4) a polymerizable compound, (4-1) a polymer, and (5) a modified substance contained in the composition of the present embodiment. A group etc. are demonstrated.

<< (1) Semiconductor material >>
Examples of the (1) semiconductor material contained in the composition of the present embodiment include the following (i) to (viii).
(I) Group II-VI compound semiconductor-containing semiconductor material (ii) Group II-V compound semiconductor-containing semiconductor material (iii) Group III-V compound semiconductor-containing semiconductor material (iv) Group III-IV Semiconductor Material Containing Compound Semiconductor (v) Semiconductor Material Containing Group III-VI Compound Semiconductor (vi) Semiconductor Material Containing Group IV-VI Compound Semiconductor (vii) Semiconductor Material Containing Transition Metal-p-Block Compound Semiconductor ( viii) a semiconductor material containing a compound semiconductor having a perovskite structure

<(I) Semiconductor Material Containing Group II-VI Compound Semiconductor>
Examples of the group II-VI compound semiconductor include a compound semiconductor containing a group 2 element and a group 16 element of the periodic table, and a compound semiconductor containing a group 12 element and a group 16 element of the periodic table. You can
In addition, in this specification, a "periodic table" means a long period type periodic table.

In the following description, a compound semiconductor containing a Group 2 element and a Group 16 element is referred to as a “compound semiconductor (i-1)” and a compound semiconductor containing a Group 12 element and a Group 16 element is referred to as a “compound semiconductor (i-1)”. -2) ".

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

Further, as the compound semiconductor (i-1),
(I-1-1) A ternary compound semiconductor containing one group 2 element and two group 16 elements (i-1-2) Two group 2 elements and one group 16 element A ternary compound semiconductor (i-1-3) containing two kinds of elements and a quaternary compound semiconductor containing two kinds of group 16 elements may be used.

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

Further, as the compound semiconductor (i-2),
(I-2-1) A ternary compound semiconductor containing one group 12 element and two group 16 elements (i-2-2) two group 12 elements and one group 16 element A ternary compound semiconductor (i-2-3) including two kinds may include a quaternary compound semiconductor including two kinds of Group 12 elements and two kinds of Group 16 elements.

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

<(Ii) Semiconductor Material Containing Group II-V Compound Semiconductor>
The group II-V compound semiconductor contains a group 12 element and a group 15 element.

Among the group II-V group compound semiconductors, examples of binary compound semiconductors include, for example, 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 .

Further, as the II-V compound semiconductor,
(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 The compound semiconductor (ii-3) of the group may be a quaternary compound semiconductor containing two kinds of Group 12 elements and two kinds of Group 15 elements.

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

<(Iii) Semiconductor Material Containing Group III-V Compound Semiconductor>
The Group III-V compound semiconductor contains a Group 13 element and a Group 15 element.

Among the group III-V group compound semiconductors, binary compound semiconductors include, for example, BP, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs, InSb, AlN, or BN. Can be mentioned.

Further, as the group III-V compound semiconductor,
(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 System compound semiconductor (iii-3) A quaternary compound semiconductor containing two kinds of Group 13 elements and two kinds of Group 15 elements may be used.

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

<(Iv) Semiconductor Material Containing Group III-IV Compound Semiconductor>
The group III-IV compound semiconductor contains a group 13 element and a group 14 element.

Among the group III-IV group compound semiconductors, examples of binary compound semiconductors include B ₄ C ₃ , Al ₄ C ₃ , and Ga ₄ C ₃ .

Further, as the group III-IV compound semiconductor,
(Iv-1) ternary compound semiconductor containing one group 13 element and two group 14 elements (iv-2) ternary compound semiconductor containing two group 13 elements and one group 14 element The compound semiconductor (iv-3) of the system may be a quaternary compound semiconductor containing two kinds of Group 13 elements and two kinds of Group 14 elements.

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

<(V) Semiconductor Material Containing Group III-VI Compound Semiconductor>
The group III-VI compound semiconductor contains a group 13 element and a group 16 element.

Of the group III-VI compound semiconductors, binary compound semiconductors include, for example, 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.

Further, as the group III-VI compound semiconductor,
(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 The compound semiconductor (v-3) of the system may be a quaternary compound semiconductor containing two kinds of group 13 elements and two kinds of group 16 elements.

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

<(Vi) Semiconductor Material Containing Group IV-VI Compound Semiconductor>
The group IV-VI compound semiconductor contains a group 14 element and a group 16 element.

Among the group IV-VI compound semiconductors, examples of binary compound semiconductors include PbS, PbSe, PbTe, SnS, SnSe, or SnTe.

Further, as the group IV-VI compound semiconductor,
(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 System compound semiconductor (vi-3) A quaternary compound semiconductor containing two kinds of Group 14 elements and two kinds of Group 16 elements may be used.

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

<(Vii) Semiconductor Material Including Transition Metal-p-Block Compound Semiconductor>
The transition metal-p-block compound semiconductor contains a transition metal element and a p-block element. The "p-block element" is an element belonging to Groups 13 to 18 of the periodic table.

Among the transition metal-p-block compound semiconductors, examples of binary compound semiconductors include NiS and CrS.

Further, as the transition metal-p-block compound semiconductor,
(Vii-1) ternary compound semiconductor containing one transition metal element and two p-block elements (vii-2) ternary compound semiconductor containing two transition metal elements and one p-block element Compound semiconductor (vii-3) A quaternary compound semiconductor containing two kinds of transition metal elements and two kinds of p-block elements may be used.

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

Specific examples of the compound semiconductor of a compound semiconductor or quaternary ternary above, 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, GaInP _{s, InAlNP, InAlNAs, CuInS 2} , or InAlPAs the like.

In the composition of the present embodiment, among the above compound semiconductors, a compound semiconductor containing Cd which is a Group 12 element and a compound semiconductor containing In which is a Group 13 element are preferable. In the composition of the present embodiment, among the above compound semiconductors, the compound semiconductor containing Cd and Se and the compound semiconductor containing In and P are preferable.

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

The compound semiconductor containing In and P is preferably a binary compound semiconductor, a ternary compound semiconductor, or a quaternary compound semiconductor. Of these, InP, which is a binary compound semiconductor, is particularly preferable.

<(Viii) Semiconductor Material Including Compound Semiconductor Having Perovskite Structure>
The compound semiconductor having a perovskite structure has a perovskite type crystal structure having A, B and X as constituent components. In the following description, a compound semiconductor having a perovskite structure may be simply referred to as “perovskite compound”.

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

The perovskite compound containing A, B, and X as constituent components is not particularly limited, and may be a compound having any of a three-dimensional structure, a two-dimensional structure, and a pseudo two-dimensional structure (quasi-2D). .
In the case of a three-dimensional structure, the composition formula of the perovskite compound is represented by 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 according to the charge balance of 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 electrically neutral perovskite compound means that the charge of the perovskite compound is zero.

The perovskite compound includes an octahedron whose center is B and whose apex is X. The octahedron is represented by BX ₆ .
If perovskite compound has a 3-dimensional structure, BX ₆ contained in the perovskite compound, share one X is located at the apex in octahedral (BX _6), 2 octahedral adjacent in the crystal (BX ₆₎ By doing so, a three-dimensional network is constructed.

If perovskite compound has a two-dimensional structure, BX ₆ contained in the perovskite compound, shared by the two X located at the vertices in octahedral (BX _6), 2 octahedral adjacent in the crystal (BX ₆₎ By doing so, the ridgeline of the octahedron is shared and a two-dimensionally continuous layer is formed. The perovskite compound has a structure in which two-dimensionally continuous layers of BX ₆ and layers of A are alternately laminated.

In the present specification, the crystal structure of the perovskite compound can be confirmed by an X-ray diffraction pattern.

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

When the perovskite compound has a three-dimensional perovskite type crystal structure, a peak derived from (hkl) = (001) is confirmed at a position of 2θ = 13 to 16 °, or a position of 2θ = 20 to 23 ° In addition, it is preferable that a peak derived from (hkl) = (110) is confirmed.

When the perovskite compound has a two-dimensional perovskite type crystal structure, a peak derived from (hkl) = (002) is usually confirmed at the position of 2θ = 1 to 10 ° in the X-ray diffraction pattern. Further, it is preferable to confirm a peak derived from (hkl) = (002) at a 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 ion, organic ammonium ion, and amidinium ion.

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

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

The alkyl groups represented by R ⁶ to R ⁹ may each independently be linear or branched. 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 each an alkyl group, the number of carbon atoms is independently 1 to 20, usually 1 to 4, preferably 1 to 3, and more preferably 1. Is more preferable.

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, independently of each other, 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 preferably each independently a hydrogen atom or an alkyl group.

When the perovskite compound contains, as A, an organic ammonium ion represented by the above formula (A3), it is preferable that the number of alkyl groups and cycloalkyl groups contained in the formula (A3) be small. In addition, the number of carbon atoms of the alkyl group and the cycloalkyl group which can be included in the formula (A3) is preferably small. Thereby, a perovskite compound having a three-dimensional structure with high emission intensity can be obtained.

In the organic ammonium ion represented by the 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. In the organic ammonium ion of the formula ^(A3), one of R 6 ~ ^{R 9} is an alkyl group having 1 to 3 carbon ^atoms, three of R 6 ~ ^{R 9} is a hydrogen atom More preferably.

The alkyl group of R ⁶ to R ⁹ is a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group. , Neopentyl group, tert-pentyl group, 1-methylbutyl group, n-hexyl group, 2-methylpentyl group, 3-methylpentyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, n-heptyl group Group, 2-methylhexyl group, 3-methylhexyl group, 2,2-dimethylpentyl group, 2,3-dimethylpentyl group, 2,4-dimethylpentyl group, 3,3-dimethylpentyl group, 3-ethylpentyl group Group, 2,2,3-trimethylbutyl group, n-octyl group, isooctyl group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group Dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group can be exemplified.

The cycloalkyl group of R 6 ^~ R ^9, include those independently R ^{6 ~} exemplified alkyl group having 3 or more carbon atoms in the alkyl group R ⁹ is to form a ring. Examples include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, norbornyl group, isobornyl group, 1-adamantyl group, 2-adamantyl group, tricyclodecyl group. Etc. can be illustrated.

Examples of the organic ammonium ion represented by A include 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 ⁺ (propyl). It is also preferably an ammonium ion), more preferably CH ₃ NH ₃ ⁺ or C ₂ H ₅ NH ₃ ⁺ , and 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 are each independently a hydrogen atom, an alkyl group which may have an amino group as a substituent, or a cycloalkyl which may have an amino group as a substituent. Represents a group.

The alkyl groups represented by R ¹⁰ to R ¹³ may each independently be linear or branched. 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 independently 1 to 20, usually 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, independently of each other, 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 of R ¹⁰ to R ¹³ include the same groups as the alkyl groups exemplified in R ⁶ to R ⁹ each independently.
Specific examples of the cycloalkyl group of R ¹⁰ to R ¹³ include the same groups as the cycloalkyl group exemplified in R ⁶ to R ⁹ each independently.

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

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

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 R ¹⁰ is an alkyl group having 1 to 3 carbon atoms. More preferably, it is a group and R ¹¹ to R ¹³ are hydrogen atoms.

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

In the perovskite compound, when A is an organic ammonium ion having 4 or more carbon atoms or an amidinium ion having 4 or more carbon atoms, the perovskite compound has either a two-dimensional structure or a pseudo two-dimensional (quasi-2D) structure. Have one or both. In this case, the perovskite compound can have a two-dimensional structure or a pseudo-two-dimensional structure in a part or the whole of the crystal.
When a plurality of two-dimensional perovskite type crystal structures are laminated, it becomes equivalent to a three-dimensional perovskite type crystal structure (references: P. PBoix et al., J. Phys. Chem. Lett. 2015, 6, 898-907, etc.).

A of the perovskite compound is preferably a cesium ion or an amidinium ion.

(Component B)
B constituting the perovskite compound may be one or more kinds of 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 at least one metal ion selected from the group consisting of lead and tin, and even more preferably lead.

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

As the halide ion, chloride ion, bromide ion, fluoride ion, iodide ion can be mentioned. X preferably contains bromide ion or iodide ion, more preferably contains bromide ion, and further preferably contains bromide ion and iodide ion.

When X is two or more kinds of halide ions, the content ratio of halide ions can be appropriately selected depending on the emission wavelength. For example, a combination of bromide ion and chloride ion or a combination of bromide ion and iodide ion can be used.
X is preferably a combination of bromide ion and iodide ion.

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

A perovskite compound in which X is a bromide ion can emit fluorescence having a maximum intensity peak in a wavelength range of usually 480 nm or more, preferably 500 nm or more, more preferably 520 nm or more.

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

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

The perovskite compound in which X is an iodide ion can emit fluorescence having a maximum intensity peak in a wavelength range of usually 520 nm or more, preferably 530 nm or more, more preferably 540 nm or more.

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

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

A perovskite compound in which X is a chloride ion can emit fluorescence having a maximum intensity peak in a wavelength range of usually 300 nm or more, preferably 310 nm or more, more preferably 330 nm or more.

Further, the perovskite compound in which X is a chloride ion 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 value and the lower limit value of the above wavelength range can be arbitrarily combined.

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

(Exemplary perovskite compound having a three-dimensional structure)
Preferred examples of the perovskite compound having 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 and (H ₂ N═CH—NH ₂ ) PbI ₃ may be mentioned.

Preferable examples of the perovskite compound having 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 ) Can also be mentioned.

Preferred examples of the three-dimensional perovskite compound 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) can also be mentioned.

Preferred examples of the three-dimensional perovskite compound include CsPb _(1-a) Na _a Br _{(3 + δ)} (0 <a ≦ 0.7, −0.7 ≦ δ <0) and CsPb _(1-a) Li. There can also be mentioned _a Br _{(3 + δ)} (0 <a ≦ 0.7, −0.7 ≦ δ <0).

Preferable examples of the three-dimensional perovskite compound 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) can also be mentioned.

As a preferable example of the perovskite compound having a three-dimensional structure, (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) can also be mentioned. .

Preferred examples of the three-dimensional perovskite compound include CsPbBr ₃ , CsPbCl ₃ , CsPbI ₃ , CsPbBr _(3-y) I _y (0 <y <3), CsPbBr _(3-y) Cl _y (0 <y < 3) can also be mentioned.

Preferred examples of the perovskite compound having 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) and CH ₃ NH ₃ Pb _(1-a) Mg _a Br ₃ (0 <a ≦ 0.7) can also be mentioned.

Preferred examples of perovskite compound having a three-dimensional structure _{_{is, 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) Mna _a Br ₃ (0 <a ≦ 0.7) ) And CsPb _(1-a) Mg _a Br ₃ (0 <a ≦ 0.7) can also be mentioned.

Preferred examples of the three-dimensional perovskite compound are 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- _{) 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) may also be mentioned.

Preferable examples of the three-dimensional perovskite compound include (H ₂ N═CH—NH ₂ ) Zn _a Br ₃ (0 <a ≦ 0.7), (H ₂ N═CH—NH ₂ ) Mga _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 three-dimensional perovskite compounds described above, CsPbBr ₃ , CsPbBr _(3-y) I _y (0 <y <3), and (H ₂ N = CH—NH ₂ ) PbBr ₃ are more preferable, and (H ₂ N Further preferred is ═CH—NH ₂ ) PbBr ₃ .

(Examples of perovskite compounds having a two-dimensional structure)
Preferred examples of the perovskite compound having a two-dimensional structure include (C ₄ H ₉ NH ₃ ) ₂ PbBr ₄ , (C ₄ H ₉ NH ₃ ) ₂ PbCl ₄ , (C ₄ H ₉ NH ₃ ) ₂ PbI ₄ , and (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) can be mentioned.

As a preferable example of the perovskite compound having a two-dimensional structure, (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) can also be mentioned.

As a preferable example of the perovskite compound having a two-dimensional structure, (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) can also be mentioned.

As a preferable example of the perovskite compound having a two-dimensional structure, (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) can also be mentioned.

Preferable examples of the two-dimensional perovskite compound also include (C ₄ H ₉ NH ₃ ) ₂ PbBr ₄ and (C ₇ H ₁₅ NH ₃ ) ₂ PbBr ₄ .

Preferred examples of the two-dimensional perovskite compound 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) can also be mentioned.

Preferable examples of the perovskite compound having a two-dimensional structure include (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Zn _a Br ₄ (0 <a ≦ 0.7), (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Mg _a Br ₄ (0 <a ≦ 0.7), (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Co _a Br ₄ (0 <a ≦ 0.7), ( _{_{_{_{C 4 H 9 NH 3) 2}}}} Pb (1-a) Mn a Br 4 (0 <a ≦ 0.7) may also be mentioned.

Preferable examples of the perovskite compound having a two-dimensional structure include (C ₇ H ₁₅ NH ₃ ) ₂ Pb _(1-a) Zn _a Br ₄ (0 <a ≦ 0.7), (C ₇ H ₁₅ NH ₃ ) ₂ Pb _(1-a) Mg _a Br ₄ (0 <a ≦ 0.7), (C ₇ H ₁₅ NH ₃ ) ₂ Pb _(1-a) Co _a Br ₄ (0 <a ≦ 0.7), ( _{_{_{_{C 7 H 15 NH 3) 2}}}} Pb (1-a) Mn a Br 4 (0 <a ≦ 0.7) may also be mentioned.

As a preferable example of the perovskite compound having a two-dimensional structure, (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) can also be mentioned.

As a preferable example of the perovskite compound having a two-dimensional structure, (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) can also be mentioned.

(Particle size of semiconductor material)
When the (1) semiconductor material contained in the composition is in a particulate form, the average particle size of the particulate (1) semiconductor material (hereinafter referred to as semiconductor particles) is particularly limited as long as it has the effect of the present invention. Not done. The average particle size of the semiconductor particles is preferably 1 nm or more because the crystal structure can be maintained well. The average particle diameter of the semiconductor particles is more preferably 2 nm or more, further preferably 3 nm or more.

Further, the average particle size of the semiconductor particles is preferably 10 μm or less because the semiconductor material is unlikely to settle and the desired light emitting characteristics are easily maintained. The average particle diameter of the semiconductor particles is more preferably 1 μm or less, further preferably 500 nm or less. The “emission characteristic” refers to optical properties such as quantum yield of converted light, emission intensity, and color purity obtained by irradiating light-emitting semiconductor particles with excitation light. The color purity can be evaluated by the full width at half maximum of the spectrum of converted light.

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

In the present specification, the average particle size of semiconductor particles can be measured by, for example, a transmission electron microscope (hereinafter, also referred to as TEM) or a scanning electron microscope (hereinafter, also referred to as SEM). Specifically, the average particle diameter can be obtained by measuring the maximum Feret diameter of 20 semiconductor particles by TEM or SEM and calculating the average maximum Feret diameter which is the arithmetic mean value of the measured values. .
In the present specification, the “maximum Feret diameter” means the maximum distance between two parallel straight lines sandwiching a semiconductor particle on a TEM or SEM image.

The median diameter (D50) of semiconductor particles is not particularly limited as long as it has the effect of the present invention. The thickness is preferably 3 nm or more because the crystal structure can be favorably maintained. The median diameter of the semiconductor particles is more preferably 4 nm or more, further preferably 5 nm or more.

Further, the median diameter (D50) of the semiconductor particles is preferably 5 μm or less because the semiconductor material is less likely to settle and the desired light emission characteristics are easily maintained. The median diameter of the semiconductor particles is more preferably 500 nm or less, further preferably 100 nm or less.

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

In the present specification, the particle size distribution of semiconductor particles can be measured by, for example, TEM or SEM. Specifically, the maximum Feret diameter of 20 semiconductor particles is observed by TEM or SEM, and the median diameter (D50) can be obtained from the distribution of the maximum Feret diameter.

In the present embodiment, the above (1) semiconductor material may be used alone or in combination of two or more.

<< (2) Surface modifier >>
(2) The surface modifier is at least one compound or ion selected from the group consisting of a tertiary amine, a tertiary ammonium cation, and a salt formed from a tertiary ammonium cation, and in the composition, ( 1) It is located on the surface of the semiconductor material, and (1) acts as a surface modifier (also called a capping ligand) of the semiconductor material. More specifically, (2) the surface modifier preferably covers at least a part of the surface of (1) the semiconductor material. (2) When the surface modifier serves as a surface modifier and covers at least part of the surface of (1) the semiconductor material, (1) the heat resistance of the semiconductor material is improved.

In the present embodiment, (1) the surface modifier that covers at least a part of the surface of the semiconductor material can be confirmed by, for example, observing the composition using 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 a tertiary amine represented by the following formula (A5).

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, and a nitro group. The hydrogen atoms contained in R ⁴¹ to R ⁴³ may each independently be substituted with a halogen atom.

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

The alkyl group of R ⁴¹ to R ⁴³ is a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group. , Neopentyl group, tert-pentyl group, 1-methylbutyl group, n-hexyl group, 2-methylpentyl group, 3-methylpentyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, n-heptyl group Group, 2-methylhexyl group, 3-methylhexyl group, 2,2-dimethylpentyl group, 2,3-dimethylpentyl group, 2,4-dimethylpentyl group, 3,3-dimethylpentyl group, 3-ethylpentyl group Group, 2,2,3-trimethylbutyl group, n-octyl group, isooctyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, -Undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-icosyl group, etc. Take as an example. Further, the n-alkyl group may further have an alkyl group as a side chain to form a branched chain.

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

The aryl group of R ⁴¹ to R ⁴³ includes a phenyl group which may have a substituent, a naphthyl group which may have a substituent, an anthracenyl group which may have a substituent, and a substituent which has a substituent. And fluorenyl group. Here, the substituent is a hydrocarbon group, and the hydrocarbon group can be substituted at any substitution position within the range of 20 or less carbon atoms, and the substitution position may be plural. The hydrocarbon group as a substituent may have an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, or a substituent which may have a substituent. Examples include good aryl groups and the like.

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

Examples of the alkynyl group of R ⁴¹ to R ⁴³ include ethynyl group, propynyl group, butynyl group, pentynyl group, hexynyl group, heptynyl group, octynyl group, nonynyl group, decynyl group, undecynyl group, dodecynyl group, tridecynyl group, tetradecynyl group, Examples include pentadecynyl group, hexadecynyl group, heptadecynyl group, octadecynyl group, nonadecynyl group and icosinyl group.

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

Further, the sum of the number of carbon atoms of the organic groups of R ⁴¹ to R ⁴³ is preferably 50 or less, more preferably 30 or less, and further preferably 25 or less. When the sum of the number of carbon atoms of the organic groups of R ⁴¹ to R ⁴³ is less than or equal to the above upper limit, the size of the tertiary amine becomes (1) an appropriate size for coating the semiconductor material, resulting in (1) The heat resistance of the semiconductor material is improved.

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

As such a combination of R ⁴¹ , R ⁴² and R ⁴³ , R ⁴¹ and R ⁴² are each independently an alkyl group selected from the group consisting of a methyl group, an ethyl group and an n-propyl group, and R ⁴³ is It is preferably an alkyl group selected from the group consisting of an n-hexadecanyl group, an n-heptadecanyl group, an n-octadecanyl group, an n-nonadecanyl group and an n-icosanyl group.

Examples of the compound of formula (A5) include Nn-octyldimethylamine, N, N-dimethyldecylamine, N, N-dimethyllaurylamine, N, N-dimethylmyristylamine, N, N-dimethylhexadecylamine, N, N-dimethylstearylamine, N, N-dimethyl-n-octadecylamine, didecylmethylamine, N, N-di-n-octylmethylamine, triheptylamine, N-methyldidodecylamine, tri-n -Octylamine and trinonylamine are listed, and from the viewpoint of improving durability, Nn-octyldimethylamine, N, N-dimethyldecylamine, N, N-dimethyllaurylamine, N, N-dimethylmyristylamine, N, N-dimethylhexadecylamine, N, N-dimethylstearylamine, N, N-dimethyl Preferably n- octadecylamine, N, N-dimethyl -n- octadecylamine are most preferred.

<Tertiary Ammonium Cation, Salt Formed from Tertiary Ammonium Cation>
Examples of the tertiary ammonium cation include a tertiary ammonium cation represented by the following formula (A6). However, in the composition of the present embodiment, when the semiconductor material (1) is a perovskite compound, the constituent component A of the perovskite compound and (2) the tertiary ammonium cation as a surface modifier are different.

In the above formula ^{^{(A6), R 41 ~ R}} 43 show the same group as ^R 41 ^{~ R 43} the above formula (A5) has.

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, a halide ion or a carboxylate ion is preferable. Examples of the halide ion include bromide ion, chloride ion, iodide ion, and fluoride ion.

In the present embodiment, the above-mentioned (2) surface modifier may be used alone or in combination of two or more kinds.

<< (6) Other surface modifiers >>
(6) The other surface modifier is at least one compound or ion selected from the group consisting of carboxylic acid, carboxylate ion and carboxylate salt.

(6) The other surface modifier is a surface modifier other than the above (2) surface modifier, and is (1) located on the surface of the semiconductor material in the composition of the present embodiment, and (1) the semiconductor material. Acts as a surface modifier of. More specifically, (6) the other surface modifier preferably covers at least a part of the surface of (1) the semiconductor material. (6) By using at least a part of the surface of the semiconductor material (1) as a surface modifier with another surface modifier, (1) the heat resistance of the semiconductor material is improved.

In the present embodiment, (1) the other surface modifier that covers at least a part of the surface of the semiconductor material can be confirmed by observing the composition using, for example, SEM or TEM. it can. Further, detailed element distribution can be analyzed by EDX measurement using SEM or TEM.

<Carboxylic acid, carboxylate ion, carboxylate salt>
The carboxylate ion, which is a surface modifier, is represented by the following formula (A2). The carboxylate salt, which is a surface modifier, is a salt containing an ion represented by the following formula (A2).
^{_{^{R 5 -CO 2 - ··· (A2}}} )

Examples of the carboxylic acid that is the surface modifier include a carboxylic acid having a proton (H ⁺ ) bonded to the carboxylate anion represented by (A2) above.

In the ion represented by the formula (A2), R ⁵ represents a monovalent hydrocarbon group. The hydrocarbon group represented by R ⁵ may be either 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 alkyl group represented by R ⁵ usually has 1 to 20 carbon atoms, preferably 5 to 20 carbon atoms, and more preferably 8 to 20 carbon atoms.

The number of carbon atoms of the cycloalkyl group is usually 3 to 30, preferably 3 to 20, and 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 unsaturated hydrocarbon group represented by R ⁵ usually has 2 to 20 carbon atoms, preferably 5 to 20 carbon atoms, and more preferably 8 to 20 carbon atoms.

R ⁵ is preferably an alkyl group or an unsaturated hydrocarbon group. The unsaturated hydrocarbon group is preferably an alkenyl group.

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

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

The oleate anion is preferable as the carboxylate anion represented by the formula (A2).

When the carboxylate anion forms a salt, the counter cation is not particularly limited, but preferable examples include an alkali metal cation, an alkaline earth metal cation, and an ammonium cation.

Oleic acid is preferable as the carboxylic acid as the surface modifier.
<< (3) Solvent >>
The solvent (3) contained in the composition of the present embodiment is not particularly limited as long as it is a medium in which (1) the semiconductor material can be dispersed. The solvent contained in the composition of this embodiment is preferably (1) a solvent in which the semiconductor material is difficult to dissolve.

The term “solvent” as used herein refers to a substance that is in a liquid state at 1 atm and 25 ° C. However, the solvent does not include a polymerizable compound and a polymer described later.

Examples of the solvent include the following (a) to (k).
(A): Ester (b): Ketone (c): Ether (d): Alcohol (e): Glycol ether (f): Organic solvent having an amide group (g): Organic solvent having a nitrile group (h): Organic solvent having a carbonate group (i): halogenated hydrocarbon (j): hydrocarbon (k): dimethyl sulfoxide

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

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

Examples of the ether (c) include diethyl ether, methyl-tert-butyl ether, diisopropyl ether, dimethoxymethane, dimethoxyethane, 1,4-dioxane, 1,3-dioxolane, 4-methyldioxolane, tetrahydrofuran, methyltetrahydrofuran, anisole and phenetole. Etc. can be mentioned.

(D) As alcohol, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, tert-butanol, 1-pentanol, 2-methyl-2-butanol, methoxypropanol, diacetone alcohol , Cyclohexanol, 2-fluoroethanol, 2,2,2-trifluoroethanol, 2,2,3,3-tetrafluoro-1-propanol and the like.

Examples of (e) glycol ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, and triethylene glycol dimethyl ether.

(F) Examples of the organic solvent having an amide group include N, N-dimethylformamide, acetamide, N, N-dimethylacetamide and the like.

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

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

(I) Examples of halogenated hydrocarbons include methylene chloride and chloroform.

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

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

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

In the composition of the present embodiment, the above solvent may be used alone or in combination of two or more.

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

In the present specification, the “polymerizable compound” means a monomer compound (monomer) having a polymerizable group. For example, the polymerizable compound may include a monomer that is in a liquid state at 1 atmosphere and 25 ° C.

For example, when the composition is produced at room temperature under normal pressure, the polymerizable compound is not particularly limited. Examples of the polymerizable compound include known polymerizable compounds such as styrene, acrylic acid ester, methacrylic acid ester, and acrylonitrile. Among them, as the polymerizable compound, one or both of acrylic acid ester and methacrylic acid ester, which are monomers of the acrylic resin, are preferable.

In the composition of the present embodiment, the polymerizable compound may be used alone or in combination of two or more.

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

<< (4-1) Polymer >>
The polymer contained in the composition of the present embodiment is preferably a polymer having a low solubility of (1) the semiconductor material of the present embodiment at the temperature for producing the composition of the present embodiment.

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

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

The weight average molecular weight of the (4-1) polymer is preferably 100 to 1200000, more preferably 1000 to 800000, and further preferably 5000 to 150,000.

In the present specification, the “weight average molecular weight” means a polystyrene conversion value measured by a gel permeation chromatography (GPC) method.

In the present embodiment, the above-mentioned (4-1) polymer may be used alone or in combination of two or more kinds.

<< (5) Modified body group >>
(5) The modified product group includes silazane, a silazane modified product, a compound represented by the formula (C1) described below, a modified compound of the compound represented by the formula (C1), and a compound represented by the formula (C2) described below. Compound, a modified product of the compound represented by the formula (C2), a compound represented by the formula (A5-51) described later, a modified product of the compound represented by the formula (A5-51), One or more selected from the group consisting of a compound represented by the formula (A5-52), a modified product of the compound represented by the formula (A5-52), sodium silicate, and a modified product of sodium silicate; It is a compound.

In the composition, it is preferable that (5) the modified body group form a shell structure with (2) a surface modifying agent-coated (1) semiconductor material as a core. Specifically, it is preferable that (5) the modified body group is coated on (1) the surface of the semiconductor material, (2) at least part of the surface of the surface modifier, and (2) the surface. At least a part of the surface of the semiconductor material which is not covered with the modifier (1) may be covered.

In the present embodiment, the composition of (1) the semiconductor material or (2) the surface modifier is coated with at least a part of the surface, and the composition of the modified body is observed, for example, by SEM or TEM. It can be confirmed by Further, detailed element distribution can be analyzed by EDX measurement using SEM or TEM.

As used herein, the term “modified” means that a silicon compound having a Si—N bond, a Si—SR bond (R is a hydrogen atom or an organic group) or a Si—OR bond (R is a hydrogen atom or an organic group) is hydrolyzed. Then, a silicon compound having a Si—O—Si bond is produced. The Si-O-Si bond may be formed by an intermolecular condensation reaction or an intramolecular condensation reaction.

In the present specification, the “modified form” refers to 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 a Si-N-Si bond. The silazane may be linear, branched or cyclic.

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

As used herein, the term "low molecular weight" means that the number average molecular weight is less than 600.
Further, in the present specification, “polymer” means that the number average molecular weight is 600 or more and 2000 or less.

In the present specification, the “number average molecular weight” means a polystyrene conversion value measured by a gel permeation chromatography (GPC) method.

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

In formula (B1), R ¹⁴ and R ¹⁵ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, or a cycloalkyl having 3 to 20 carbon atoms. Represents a group, an aryl group having 6 to 20 carbon atoms, or an alkylsilyl group having 1 to 20 carbon atoms.

R ¹⁴ and R ¹⁵ may have a substituent such as an amino group. Plural R15s may be the same or different.

Examples of the low-molecular silazane represented by the formula (B1) include 1,3-divinyl-1,1,3,3-tetramethyldisilazane, 1,3-diphenyltetramethyldisilazane, and 1,1,1, 3,3,3-hexamethyldisilazane can be mentioned.

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

Wherein ^{(B2), R 14,} and ^{R 15} are the same as ^{R 14,} and ^{R 15} in the formula (B1).

A plurality of R ^14's may be the same or different.
A plurality of R ^15's may be the same or different.

In formula (B2), n ₁ represents an integer of 1 or more and 20 or less. n ₁ may be an integer of 1 or more and 10 or less, or 1 or 2.

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

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

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

Polysilazane is a polymer compound having a Si—N—Si bond. The constitutional unit of the polysilazane represented by the formula (B3) may be one kind or plural kinds.

Wherein ^{(B3), R 14,} and ^{R 15} are the same as ^{R 14,} and ^{R 15} in the formula (B1).

In formula (B3), * represents a 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.

M represents an integer of 2 or more and 10000 or less.

The polysilazane represented by the formula (B3) may be, for example, perhydropolysilazane in which all of R ¹⁴ and R ¹⁵ are hydrogen atoms.

Moreover, the polysilazane represented by the formula (B3) may be, for example, an organopolysilazane in which at least one R ¹⁵ is a group other than a hydrogen atom. Perhydropolysilazane and organopolysilazane may be appropriately selected depending on the intended use, and they may 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 preferable.

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

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

When the polysilazane contains a plurality of structures represented by the formula (B4) in the molecule, the bond of the structure represented by the formula (B4) is a bond of the structure represented by another formula (B4). It may be directly connected to the hand.

It is bonded to any of the bond of the polysilazane represented by the formula (B3), the bond of the constitutional unit of the polysilazane represented by the formula (B3), and the bond of the structure represented by the other formula (B4). R ¹⁴ is bonded to the bond of the non-N atom.

It is bonded to any of the bond of the polysilazane represented by the formula (B3), the bond of the constitutional unit of the polysilazane represented by the formula (B3), and the bond of the structure represented by the other formula (B4). R ¹⁵ is bonded to the bond of the non-Si atom.

n ₂ represents an integer of 1 or more and 10000 or less. n ₂ may be an integer of 1 or more and 10 or less, or 1 or 2.

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

A commercially available product may be used as the polysilazane. (Manufactured by the company), AZNN-120-20, Durazane (registered trademark) 1500 Slow Cure, Durazane 1500 Rapid Rapid, Durazane 1800, and Durazane 1033 (manufactured by Merck Performance Materials Co., Ltd.).

The polysilazane is preferably AZNN-120-20, Durazane1500 Slow Cure, Durazane1500 Rapid Cure, more preferably Durazane1500 Slow Cure, Durazane1500 Rapidzur, and further preferably Durazane1500.

In the modified low molecular weight silazane represented by the formula (B2), the ratio of silicon atoms not bonded to nitrogen atoms is preferably 0.1 to 100% with respect to all silicon atoms. Further, the ratio of silicon atoms not bonded to nitrogen atoms is more preferably 10 to 98%, further preferably 30 to 95%.

The “ratio of silicon atoms not bonded to nitrogen atoms” is ((Si (mol) − (N (mol) in SiN bond) / Si (mol) × 100), using the measured value described later. Considering the reforming reaction, the “ratio of silicon atoms not bonded to nitrogen atoms” means the “ratio of silicon atoms contained in the siloxane bond generated in the modification treatment”.

In the modified polysilazane represented by the formula (B3), the ratio of silicon atoms not bonded to nitrogen atoms is preferably 0.1 to 100% with respect to all silicon atoms. Further, the ratio of silicon atoms not bonded to nitrogen atoms is more preferably 10 to 98%, further preferably 30 to 95%.

In the modified polysilazane having the structure represented by the formula (B4), the ratio of silicon atoms not bonded to nitrogen atoms is preferably 0.1 to 99% with respect to all silicon atoms. Further, the proportion of silicon atoms not bonded to nitrogen atoms is more preferably 10 to 97%, further preferably 30 to 95%.

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

The “ratio of silicon atoms not bonded to nitrogen atoms” of the modified product, which is determined by using the value measured by the above method, is preferably 0.1 to 99%, and 10 to 99%. Is more preferable, and further preferably 30 to 95%.

(5) The silazane contained in the modified product group or a modified product thereof is not particularly limited, but organopolysilazane or a modified product thereof is preferable from the viewpoint of improving dispersibility and suppressing aggregation.

Examples of the organopolysilazane are represented by the formula (B3), and 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 3 to It may be a cycloalkyl group having 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an organopolysilazane which is an alkylsilyl group having 1 to 20 carbon atoms.

In addition, the organopolysilazane includes, for example, a structure represented by the formula (B4), at least one bond is bonded to R ¹⁴ or R ^15, and at least one of R ¹⁴ and R ¹⁵ is the number of carbon atoms. An alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkylsilyl group having 1 to 20 carbon atoms It may be some organopolysilazane.

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

(2. Compound represented by formula (C1), compound represented by formula (C2))
(5) The modified compound group may be a compound represented by the following formula (C1) or a compound represented by the following formula (C2).

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 are each independently 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. It represents up to 20 unsaturated hydrocarbon groups.

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

In 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 are each independently a halogen atom or an amino group. May be replaced with.

Examples of the halogen atom which may be substituted 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 a fluorine atom, a chlorine atom and a bromine atom. , And iodine atoms are preferable, and fluorine atoms are preferable from the viewpoint of chemical stability.

In the formulas (C1) and (C2), a is an integer of 1 to 3.
When a is 2 or 3, a plurality of Y ^{5 s} may be the same or different.
When a is 2 or 3, a plurality of R ^30's may be the same or different.
When a is 2 or 3, a plurality of R ^32's may be the same or different.
When a is 1 or 2, a plurality of R ^31's 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 the formula (C1), when Y ⁵ is an oxygen atom, the number of carbon atoms of the alkyl group represented by R ³⁰ is 1 to 20 because reforming proceeds rapidly. preferable. The number of carbon atoms of the alkyl group represented by R ³⁰ is more preferably 1 to 3, and even more preferably 1.

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

In the compound represented by the formula (C1), Y ⁵ is preferably an oxygen atom because reforming proceeds rapidly.

In the compound represented by the formula (C2), the number of carbon atoms of the alkyl group represented by R ³⁰ and R ³² is preferably 1 to 20 each independently because reforming proceeds rapidly. Further, the number of carbon atoms of the alkyl group represented by R ³⁰ and R ³² is more preferably independently 1 to 3, and further preferably 1.

In both the compound represented by the formula (C1) and the compound represented by the formula (C2), the alkyl group represented by R ³¹ preferably has 1 to 5 carbon atoms and 1 to 2 carbon atoms. More preferably, it is more preferably 1.

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

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

When the hydrogen atoms in the cycloalkyl group represented by R ³⁰ , R ³¹ and R ³² are each independently substituted with an alkyl group, the cycloalkyl group has 4 or more carbon atoms. The alkyl group in which the hydrogen atom in the cycloalkyl group may be substituted has 1 to 27 carbon atoms.

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

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

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

The unsaturated hydrocarbon group represented by R ³⁰ , R ³¹ and R ³² is preferably an alkenyl group, and 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 linear or branched alkyl groups exemplified in the groups represented by R ⁶ to R ⁹ and having one carbon atom An example is one in which a single bond (C—C) is replaced with a double bond (C═C). The position of the double bond in the alkenyl group is not limited.

Preferable examples of such alkenyl group include, for example, ethenyl group, propenyl group, 3-butenyl group, 2-butenyl group, 2-pentenyl group, 2-hexenyl group, 2-nonenyl group, 2-dodecenyl group, 9 An octadecenyl group.

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

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

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

Specific examples of the compound represented by the formula (C1) include tetraethoxysilane, tetramethoxysilane, tetrabutoxysilane, tetrapropoxysilane, tetraisopropoxysilane, 3-aminopropyltriethoxysilane, and 3-aminopropyltrisilane. Methoxysilane, trimethoxyphenylsilane, ethoxytriethylsilane, methoxytrimethylsilane, methoxydimethyl (phenyl) silane, pentafluorophenylethoxydimethylsilane, trimethylethoxysilane, 3-chloropropyldimethoxymethylsilane, (3-chloropropyl) diethoxy ( Methyl) silane, (chloromethyl) dimethoxy (methyl) silane, (chloromethyl) diethoxy (methyl) silane, diethoxydimethylsilane, dimethoxydimethylsilane, dime Xydiphenylsilane, dimethoxymethylphenylsilane, diethoxydiphenylsilane, dimethoxymethylvinylsilane, diethoxy (methyl) phenylsilane, dimethoxy (methyl) (3,3,3-trifluoropropyl) silane, allyltriethoxysilane, allyltrimethoxy Silane, (3-bromopropyl) trimethoxysilane, cyclohexyltrimethoxysilane, (chloromethyl) triethoxysilane, (chloromethyl) trimethoxysilane, dodecyltriethoxysilane, dodecyltrimethoxysilane, triethoxyethylsilane, decyltri Methoxysilane, ethyltrimethoxysilane, hexyltriethoxysilane, hexyltrimethoxysilane, hexadecyltrimethoxysilane, trimethoxy (methyl) silane, Liethoxymethylsilane, trimethoxy (1H, 1H, 2H, 2H-heptadecafluorodecyl) silane, triethoxy-1H, 1H, 2H, 2H-tridecafluoro-n-octylsilane, trimethoxy (1H, 1H, 2H, 2H -Nonafluorohexyl) silane, trimethoxy (3,3,3-trifluoropropyl) silane, 1H, 1H, 2H, 2H-perfluorooctyltriethoxysilane and the like.

Among them, as the compound represented by the formula (C1), trimethoxyphenylsilane, methoxydimethyl (phenyl) silane, dimethoxydiphenylsilane, dimethoxymethylphenylsilane, cyclohexyltrimethoxysilane, dodecyltriethoxysilane, dodecyltrimethoxysilane. , Decyltrimethoxysilane, hexyltriethoxysilane, hexyltrimethoxysilane, hexadecyltrimethoxysilane, trimethoxy (1H, 1H, 2H, 2H-heptadecafluorodecyl) silane, triethoxy-1H, 1H, 2H, 2H-tri Decafluoro-n-octylsilane, trimethoxy (1H, 1H, 2H, 2H-nonafluorohexyl) silane, trimethoxy (3,3,3-trifluoropropyl) silane, 1H, 1H, 2H, H-perfluorooctyltriethoxysilane, tetraethoxysilane, tetramethoxysilane, tetrabutoxysilane and tetraisopropoxysilane are preferable, tetraethoxysilane, tetramethoxysilane, tetrabutoxysilane and tetraisopropoxysilane are more preferable, and tetramethoxy Silane is most preferred.

Further, as the compound represented by the formula (C1), dodecyltrimethoxysilane, trimethoxyphenylsilane, 1H, 1H, 2H, 2H-perfluorooctyltriethoxysilane, trimethoxy (1H, 1H, 2H, 2H-nona It may be fluorohexyl) silane.

(3. Compound represented by formula (A5-51), compound represented by formula (A5-52))
(5) The modified compound group may be a compound represented by the following formula (A5-51) or a compound represented by the following formula (A5-52).

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

In formulas (A5-51) and (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 alkyl group has usually 1 to 20 carbon atoms, preferably 5 to 20 carbon atoms, and more preferably 8 to 20 carbon atoms.

When R ¹²² to R ¹²⁶ are cycloalkyl groups, the cycloalkyl group may have an alkyl group as a substituent. The cycloalkyl group has usually 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms, and more preferably 3 to 11 carbon atoms. 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 each independently substituted with a halogen atom or an amino group.

Examples of the halogen atom, which may be substituted for the hydrogen atom contained in the alkyl group and cycloalkyl group represented by R ¹²² to R ¹²⁶ , include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. A fluorine atom is preferable from the viewpoint of stability.

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

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

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

When R ¹²⁵ and R ¹²⁶ are an alkoxy group, a methoxy group, an ethoxy group, a butoxy group and the like can be mentioned, and a methoxy group is preferable.

Divalent hydrocarbon group represented by A ^C may be any groups from the hydrocarbon compound removal of two hydrogen atoms, said hydrocarbon compound may be an aliphatic hydrocarbon, aromatic It may be a hydrocarbon or a saturated aliphatic hydrocarbon. When ^AC is an alkylene group, it may be linear or branched. The alkylene group has usually 1 to 100 carbon atoms, preferably 1 to 20 carbon atoms, and more preferably 1 to 5 carbon atoms.

Examples of the compound represented by the formula (A5-51) include trimethoxy [3- (methylamino) propyl] silane, 3-aminopropyltriethoxysilane, 3-aminopropyldimethoxymethylsilane, and 3-aminopropyldiethoxymethylsilane. , 3-aminopropyltrimethoxysilane is preferred.

The compound represented by the formula (A5-51) is preferably 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 alkoxy groups. For example, 3-aminopropyltriethoxysilane and 3-aminopropyltrimethoxysilane are more preferable.

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

(Sodium silicate)
(5) The modified body group may be sodium silicate (Na ₂ SiO ₃ ).

ㆍ Sodium silicate undergoes hydrolysis and is modified by treatment with acid.

In the present embodiment, the above-mentioned (5) modified body group may be used alone or in combination of two or more kinds.

<Regarding the compounding ratio of each component>
In the composition of the present embodiment, the compounding ratio of (1) a semiconductor material and (2) a surface modifier can be appropriately determined according to the type of components constituting the composition and the like.
In the composition of the present embodiment, the molar ratio [(1) semiconductor material / (2) surface modifier] of (1) semiconductor material to (2) surface modifier is 0.0001 to 1,000. It may be 0.01 to 100.
The resin composition in which the range of the compounding ratio of (1) the semiconductor material and (2) the surface modifier is within the above range is (1) the aggregation of the semiconductor material is less likely to occur, and the light emitting property is also excellently exhibited. It is preferable in terms.

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

In the composition of the present embodiment, the compounding ratio of (1) the semiconductor material and (5) the modified body group may be such that (5) the modified body group exhibits the action of improving the durability. , (1) semiconductor material and (5) type of modified body group, etc.
In the composition of the present embodiment, when (1) the semiconductor material is a perovskite compound, (1) the molar ratio of the metal ion that is the B component of the semiconductor material to (5) the Si element of the modified body group [Si / B] may be 0.001 to 2000 or 0.01 to 500.

In the composition of the present embodiment, (5) the modified compound group is a silazane represented by the formula (B1) or (B2) and a modified compound thereof, and (1) the semiconductor material is a perovskite compound. , (1) the molar ratio [Si / B] of the metal ion, which is the B component of the semiconductor material, and (5) the Si of the modified body group may be 1 to 1000, or 10 to 500. It may be 20 to 300.

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

The composition in which the compounding ratio of the (1) semiconductor material and the (5) modified body group is within the above range exhibits the effect of improving the durability of the (5) modified body group particularly well. It is preferable in that

The molar ratio [Si / B] between the metal ion, which is the B component of the perovskite compound, and the Si element of the modified product can be determined by the following method.

The substance amount (B) (unit: mol) of the metal ion that is the B component of the perovskite compound is measured by inductively coupled plasma mass spectrometry (ICP-MS) to measure the mass of the metal that is the B component, and the measured value is the substance amount. Converted to.

The substance amount (Si) of the Si element of the reformer is calculated from the value obtained by converting the mass of the raw material compound of the reformer used into the substance amount and the Si amount (substance amount) contained in the unit mass of the raw material compound. . 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 substance amount (Si) of the Si element and the substance amount (B) of the metal ion that is the B component of the perovskite compound.

<Method for producing composition>
Hereinafter, the method for producing the composition of the present invention will be described with reference to embodiments. The composition of the present embodiment is not limited to that produced by the method for producing the composition of the following embodiments.

<(1) Method for manufacturing semiconductor material>
(Methods for manufacturing semiconductor materials (i) to (vii))
The semiconductor materials (i) to (vii) can be manufactured by a method of heating a mixed liquid obtained by mixing a simple substance of the elements constituting the semiconductor material or a compound of the elements constituting the semiconductor material and a fat-soluble solvent. .

Examples of the compound containing an element constituting the semiconductor material are not particularly limited, but include oxides, acetates, organometallic 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 and oxygen-containing compounds having a hydrocarbon group having 4 to 20 carbon atoms.

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 group, isobutyl group, n-pentyl group, octyl group, decyl group, dodecyl group, hexadecyl group and octadecyl group.

As an unsaturated aliphatic hydrocarbon group having 4 to 20 carbon atoms, an oleyl group can be mentioned.

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

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

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

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

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

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

The heating temperature of the above mixed solution may be appropriately set depending on the type of raw material (single substance or compound) used. The heating temperature of the mixed solution is, for example, preferably 130 to 300 ° C, more preferably 240 to 300 ° C. It is preferable for the heating temperature to be at least the above lower limit value because the crystal structure is easily unified. When the heating temperature is not higher than the above upper limit, the crystal structure of the semiconductor material that is produced is less likely to collapse, and the target product is easily obtained, which is preferable.

The heating time of the mixed solution may be appropriately set depending on the types of raw materials (single or compound) used and the heating temperature. The heating time of the mixed liquid is, for example, preferably several seconds to several hours, more preferably 1 to 60 minutes.

In the above-mentioned semiconductor material manufacturing method, by cooling the mixed solution after heating, a precipitate containing the target semiconductor material can be obtained. By separating the precipitate and washing it appropriately, the target semiconductor material can be obtained.

For the supernatant liquid from which the precipitate is separated, a solvent in which the synthesized semiconductor material is insoluble or sparingly soluble is added to reduce the solubility of the semiconductor material in the supernatant liquid to form a precipitate, and the semiconductor material contained in the supernatant liquid is added. You may collect it. Examples of the “solvent in which the semiconductor material is insoluble or sparingly soluble” include methanol, ethanol, acetone, acetonitrile and the like.

In the above-mentioned semiconductor material manufacturing method, the separated precipitate may be put in an organic solvent (eg, chloroform, toluene, hexane, n-butanol, etc.) to form a solution containing the semiconductor material.

(Method for manufacturing semiconductor material of (viii))
The manufacturing method of the semiconductor material of (viii) can be manufactured by the method described below with reference to known literatures (Nano Lett. 2015, 15, 3692-3696, ACS Nano, 2015, 9, 4533-4542).

(First manufacturing method)
As a method for producing a perovskite compound, a step of dissolving a compound containing an A component, a compound containing a B component, and a compound containing an X component, which form the perovskite compound, in a first solvent; A manufacturing method including a step of mixing two solvents.

The second solvent has a lower solubility for the perovskite compound than the first solvent.
The solubility means the solubility at the temperature at which the step of mixing the obtained solution and the second solvent is performed.

As the first solvent and the second solvent, at least two kinds selected from the group of organic solvents mentioned above as (a) to (k) can be mentioned.

For example, when performing the step of mixing the solution and the second solvent at room temperature (10 ° C. to 30 ° C.), the above-mentioned (d) alcohol, (e) glycol ether, and (f) amide group are used as the first solvent. The organic solvent which it has and (k) dimethyl sulfoxide can be mentioned.

When the step of mixing the solution and the second solvent at room temperature (10 ° C. to 30 ° C.) is performed, the second solvent may be the above-mentioned (a) ester, (b) ketone, (c) ether, or (g). ) Organic solvents having a nitrile group, (h) organic solvents having a carbonate group, (i) halogenated hydrocarbons, and (j) hydrocarbons.

Hereinafter, the first manufacturing method will be specifically described.
First, the compound containing the component A, the compound containing the component B, and the compound containing the component X are dissolved in the first solvent to obtain a solution. The “compound including the component A” may include the component X. The “compound including the component B” may include the component X.

Next, the solution obtained and the second solvent are mixed. In the step of mixing the solution and the second solvent, the (I) solution may be added to the second solvent, or the (II) second solvent may be added to the solution. Since the particles of the perovskite compound generated in the first production method are easily dispersed in the solution, it is advisable to add the solution (I) to the second solvent.

When mixing the solution and the second solvent, one may be dropped on the other. Moreover, it is good to mix a solution and a 2nd solvent, stirring.

In the step of mixing the solution and the second solvent, there is no particular limitation on the temperature of the solution and the second solvent. Since the obtained perovskite compound is easily precipitated, the temperature is preferably in the range of -20 ° C to 40 ° C, more preferably in the range of -5 ° C to 30 ° C. The temperature of the solution and the temperature of the second solvent may be the same or different.

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

As a combination of the first solvent and the second solvent, the first solvent is an organic solvent having an amide group such as N, N-dimethylacetamide or dimethyl sulfoxide, and the second solvent is a halogenated hydrocarbon or a hydrocarbon. preferable. When the first solvent and the second solvent are a combination of these solvents, for example, the solubility of the first solvent and the second solvent in the perovskite compound when performing the step of mixing at room temperature (10 ° C to 30 ° C) Is preferable because it is easy to control the difference of 100 μg / solvent 100 g to 90 g / solvent 100 g.

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

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

Note that the above-mentioned production method preferably includes the step of adding the above-mentioned surface modifier, because the particles of the perovskite compound obtained are easily and stably dispersed in the dispersion liquid.

The step of adding the surface modifier is preferably performed before the step of mixing the solution and the second solvent. Specifically, the surface modifier may be added to the first solvent, the solution, or the second solvent. Further, the surface modifier may be added to both the first solvent and the second solvent.

In addition, it is preferable that the above-mentioned manufacturing method includes a step of removing coarse particles by a method such as centrifugation or filtration after the step of mixing the solution and the second solvent. The size of the coarse particles removed in the removing step is preferably 10 μm or more, more preferably 1 μm or more, and further preferably 500 nm or more.

(Second manufacturing method)
As a method for producing a perovskite compound, a step of dissolving a compound including an A component, a compound including a B component, and a compound including an X component, which form the perovskite compound, in a high temperature third solvent, and cooling the solution. And a manufacturing method including a step.

The following will specifically describe the second manufacturing method.

First, the compound containing the component A, the compound containing the component B, and the compound containing the component X are dissolved in a high-temperature third solvent to obtain a solution. The “compound including the component A” may include the component X.
The “compound including the component B” may include the component X.
In this step, each compound may be added to and dissolved in a high temperature third solvent to obtain a solution.
Further, in this step, after adding each compound to the third solvent, the temperature may be raised to obtain a solution.

The third solvent includes a solvent capable of dissolving a compound containing the component A, which is a raw material, a compound containing the component B, and a compound containing the component X. Specifically, examples of the third solvent include the above-mentioned first solvent and second solvent.

“High temperature” means a solvent at a temperature at which each raw material dissolves. For example, the temperature of the high temperature third solvent is preferably 60 to 600 ° C., and more preferably 80 to 400 ° C.

The resulting solution is then cooled.
The cooling temperature is preferably −20 to 50 ° C., more preferably −10 to 30 ° C.
The cooling rate is preferably 0.1 to 1500 ° C./min, more preferably 10 to 150 ° C./min.

By cooling the hot solution, the perovskite compound can be precipitated due to the difference in solubility due to the temperature difference between the solutions. As a result, a dispersion liquid containing the perovskite compound is obtained.

The perovskite compound can be recovered by solid-liquid separation of the obtained dispersion liquid containing the perovskite compound. Examples of the solid-liquid separation method include the method described in the first manufacturing method.

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

Further, in the above-mentioned manufacturing method, it is preferable that after the cooling step, a step of removing coarse particles by a method such as centrifugation and filtration shown in the first manufacturing method is included.

(Third manufacturing method)
As a method for producing a perovskite compound, a step of obtaining a first solution in which a compound containing an A component constituting a perovskite compound and a compound containing a B component are dissolved, and a compound containing an X component constituting a perovskite compound are dissolved. The manufacturing method includes a step of obtaining the second solution, a step of mixing the first solution and the second solution to obtain a mixed solution, and a step of cooling the obtained mixed solution.

The following will specifically describe the third manufacturing method.

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

The fourth solvent includes a solvent capable of dissolving the compound containing the component A and the compound containing the component B. Specifically, examples of the fourth solvent include the above-mentioned third solvent.

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

Also, the compound containing the X component is dissolved in the fifth solvent to obtain the second solution. The compound containing the X component may contain the B component.

Examples of the fifth solvent include a solvent capable of dissolving the compound containing the component X.
Specifically, examples of the fifth solvent include the above-mentioned third solvent.

Next, the first solution and the second solution obtained are mixed to obtain a mixed solution. When mixing the first solution and the second solution, one may be dropped on the other. Further, it is advisable to mix the first solution and the second solution while stirring.

Then, the obtained mixed liquid is cooled.
The cooling temperature is preferably −20 to 50 ° C., more preferably −10 to 30 ° C.
The cooling rate is preferably 0.1 to 1500 ° C./min, more preferably 10 to 150 ° C./min.

By cooling the mixed solution, the perovskite compound can be precipitated due to the difference in solubility due to the difference in temperature of the mixed solution. As a result, a dispersion liquid containing the perovskite compound is obtained.

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

<< Production Method 1 of Composition >>
Hereinafter, in order to facilitate understanding of the properties of the obtained composition, the composition obtained by the method 1 for producing a composition is referred to as a “liquid composition”.

The liquid composition of the present embodiment can be produced by mixing (1) a semiconductor material and (2) a surface modifier with one or both of (3) a solvent and (4) a polymerizable compound. it can.

When (1) the semiconductor material and (2) the surface modifier and one or both of the (3) solvent and (4) polymerizable compound are mixed, it is preferable to carry out the stirring.

When mixing (1) a semiconductor material, (2) a surface modifier and (4) a polymerizable compound, there is no particular limitation on the temperature at the time of mixing. Since the semiconductor material (1) and the surface modifier (2) are easily mixed uniformly, the temperature range is preferably 0 ° C to 100 ° C, more preferably 10 ° C to 80 ° C.

((3) Method for producing liquid composition containing solvent)
The method for producing a composition containing (1) a semiconductor material, (2) a surface modifier and (3) a solvent may be, for example, the following production method (a1) or the following production method (a2). May be.

Manufacturing method (a1): A method for manufacturing a composition, which comprises: (1) mixing a semiconductor material with (3) a solvent; and (2) mixing the obtained mixture with a surface modifier.

Manufacturing method (a2): A method for manufacturing a composition including the steps of (1) mixing a semiconductor material with (2) a surface modifier, and mixing the resulting mixture with (3) a solvent.

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

When the composition of the present embodiment includes (5) modified product group, the method for producing the composition may be the production method (a3) using the following (5A) or the production method (a4). May be.
(5A): silazane, a compound represented by the formula (C1), a compound represented by the formula (C2), a compound represented by the formula (A5-51), a compound represented by the formula (A5-52), And one or more compounds selected from the group consisting of sodium silicate

In the following explanation, the above (5A) is referred to as “(5A) raw material compound”. The (5A) raw material compound becomes a (5) modified body group by performing a modification treatment.

Production method (a3): (1) a step of mixing a semiconductor material and (3) a solvent, a step of mixing the obtained mixture, (2) a surface modifier and (5A) a raw material compound, and the obtained mixture And a step of subjecting the composition to a modification treatment, to produce a composition.

Production method (a4): (1) a step of mixing a semiconductor material, (2) a surface modifier and (5A) a raw material compound, a step of mixing the obtained mixture with a (3) solvent, and the obtained mixture And a step of subjecting the composition to a modification treatment, to produce a composition.

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

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

In the mixing step included in the above-mentioned manufacturing method, the temperature is not particularly limited, but from the viewpoint of uniform mixing, it is preferably in the range of 0 ° C or higher and 100 ° C or lower, and in the range of 10 ° C or higher and 80 ° C or lower. Is more preferable.

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

(Method of applying modification treatment)
Examples of the modification treatment method include known methods such as (5A) a method of irradiating the raw material compound with ultraviolet rays, and (5A) a method of reacting the raw material compound with water vapor. In the following description, the treatment of reacting the starting compound (5A) with water vapor may be referred to as “humidification treatment”.

Above all, it is preferable to apply a humidification treatment from the viewpoint of (1) forming a stronger protective region in the vicinity of 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, more preferably 100 to 180 nm. Examples of the light source for generating 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 the humidification treatment is performed, the composition may be left standing or stirred for a certain period of time under the temperature and humidity conditions described below.

The temperature in the humidification treatment may be a temperature at which reforming progresses sufficiently. The temperature in the humidifying treatment is, for example, preferably 5 to 150 ° C., more preferably 10 to 100 ° C., and further preferably 15 to 80 ° C.

The humidity in the humidification treatment may be such that the (5A) raw material compound in the composition is sufficiently supplied with water. The humidity in the humidifying treatment is, for example, preferably 30% to 100%, more preferably 40% to 95%, and further preferably 60% to 90%. The humidity means relative humidity at the temperature at which the humidifying process is performed.

ㆍ The time required for the humidification treatment may be any time that allows the reforming to proceed sufficiently. The time required for the humidifying treatment is, for example, preferably 10 minutes or more and 1 week or less, more preferably 1 hour or more and 5 days or less, and further preferably 2 hours or more and 3 days or less.

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

The water in the humidification treatment may be supplied by circulating a gas containing water vapor in the reaction vessel, or by supplying water from the interface by stirring in an atmosphere containing water vapor.

When a gas containing water vapor is circulated in the reaction vessel, the durability of the resulting composition is improved, so that the flow rate of the gas containing water vapor is preferably 0.01 L / min or more and 100 L / min or less, and 0.1 L / min. It is more preferably 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 steam include nitrogen containing a saturated amount of steam.

(1) When the semiconductor material is a perovskite compound, (2) the surface modifier, (3) the solvent and (5) the modified body group in the method for producing the composition of the present embodiment are the same as the above-mentioned (1) semiconductor material. They may be mixed in any step included in the manufacturing method. For example, the following manufacturing method (a5) may be used, or the following manufacturing method (a6) may be used.

Production method (a5): First, a compound containing a B component, a compound containing an X component, a compound containing an A component, which constitutes a perovskite compound, (2) a surface modifier, and (5) a modified body group. A manufacturing method including a step of dissolving in a solvent to obtain a solution and a step of mixing the obtained solution and a second solvent can be mentioned.
The first solvent and the second solvent are the same as the above-mentioned solvents.

Production method (a6): A compound containing a component B, a compound containing an component X, and a compound containing component A, which constitute the perovskite compound, (2) a surface modifier, and (5) a group of modified substances at high temperature. The manufacturing method includes a step of dissolving the solution in a third solvent to obtain a solution, and a step of cooling the solution.
The third solvent is the same as the above-mentioned 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 above-mentioned (viii) method for manufacturing a semiconductor material.

((4) Method for producing liquid composition containing polymerizable compound)
The method for producing a composition containing (1) a semiconductor material, (2) a surface modifier, (4) a polymerizable compound, and (5) a group of modified compounds is, for example, the following production methods (c1) to (c3). Can be mentioned.

Production method (c1): (4) a step of dispersing (1) a semiconductor material in a polymerizable compound to obtain a dispersion, the obtained dispersion, (2) a surface modifier, and (5) a group of modified products. And a mixing step.

Production method (c2): a step of dispersing (2) a surface modifier and (5) a group of modifiers in (4) a polymerizable compound to obtain a dispersion, the obtained dispersion and (1) a semiconductor material. And a step of mixing.

Production method (c3): A production method including a step of dispersing a mixture of (1) a semiconductor material, (2) a surface modifier and (5) a group of modifiers in (4) a polymerizable compound.

In the manufacturing methods (c1) to (c3), the manufacturing method (c1) is preferable from the viewpoint of (1) enhancing dispersibility of the semiconductor material.

In the manufacturing method (c1) to (c3), in the step of obtaining each dispersion, the polymerizable compound (4) may be added dropwise to each material, or each material may be added dropwise to the polymerizable compound (4). Good.
At least one of (1) a semiconductor material, (2) a surface modifier, and (5) a modified compound group is preferably added dropwise to (4) a polymerizable compound because it is easily dispersed uniformly.

In the manufacturing methods (c1) to (c3), in each mixing step, the dispersion may be dropped onto each material, or each material may be dropped onto the dispersion.
At least one of (1) a semiconductor material, (2) a surface modifier, and (5) a modified body group is preferably added dropwise to the dispersion because it is easily dispersed uniformly.

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

The solvent that dissolves or disperses the polymer (4-1) is not particularly limited. The solvent is preferably (1) a solvent in which the semiconductor material is difficult to dissolve.
Examples of the solvent in which the polymer (4-1) is dissolved include the same solvents as the above-mentioned third solvent.

Among them, the second solvent is preferable because it has low polarity and (1) it is considered that it is difficult to dissolve the semiconductor material.

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

The method for producing the composition of the present embodiment may be the following production method (c4) or production method (c5).

Production method (c4): (1) a step of dispersing a semiconductor material in a solvent to obtain a dispersion, and a step of mixing the obtained dispersion with a polymerizable compound (4) to obtain a mixed solution, A method for producing a composition, comprising a step of mixing the obtained mixed liquid, (2) a surface modifier, and (5) a group of modified bodies.

Production method (c5): (1) a step of dispersing a semiconductor material in a solvent to obtain a dispersion liquid, the obtained dispersion liquid, (2) a surface modifier and (5A) a raw material compound are mixed and mixed. A step of obtaining a liquid, a step of subjecting the obtained mixed solution to a modification treatment (5) to obtain a mixed solution containing a group of modified bodies, and a step of mixing the obtained mixed solution with (3) a polymerizable compound And a method for producing the composition.

In the method 1 for producing a composition, when (6) another surface modifier is used, it can be added together with (2) the surface modifier.

<< Composition Manufacturing Method 2 >>
As the method for producing the composition of the present embodiment, a step of mixing (1) a semiconductor material, (2) a surface modifier, (4) a polymerizable compound, and (5) a modified body group, 4) a step of polymerizing the polymerizable compound, and a production method including the step.

The composition obtained by the method 2 for producing a composition is such that the total of (1) a semiconductor material, (2) a surface modifier, (4-1) a polymer, and (5) a modified body group is the total mass of the composition. It is preferably 90% by mass or more.

The method for producing the composition of the present embodiment includes (1) a semiconductor material, (2) a surface modifier, (3) a polymer (4-1) dissolved in a solvent, and (5). A manufacturing method including a step of mixing the modified body group and a step of (3) removing the solvent can also be mentioned.

For the mixing step included in the above-mentioned production method, the same mixing method as the method shown in the above-mentioned production method 1 of the composition can be used.

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

Production method (d1): (4) a step of dispersing (1) a semiconductor material in a polymerizable compound to obtain a dispersion, the obtained dispersion, (2) a surface modifier, and (5) a group of modified products. A production method comprising a step of mixing and a step (4) of polymerizing a polymerizable compound.

Production method (d2): (4-1) a step of dispersing a semiconductor material in (3) a solvent in which a polymer is dissolved to obtain a dispersion, the obtained dispersion, and (2) a surface modifier. (5) A manufacturing method including a step of mixing the modified body group and a step of removing the solvent.

Production method (d3): a step of dispersing (2) a surface modifier and (5) a group of modifiers in a polymerizable compound (4) to obtain a dispersion, the obtained dispersion and (1) a semiconductor material. And a step of polymerizing the polymerizable compound (4).

Production method (d4): a step of dispersing (2) a surface modifier and (5) a group of modifiers in (3) a solvent in which (4-1) a polymer is dissolved to obtain a dispersion, A manufacturing method comprising a step of mixing a dispersion and (1) a semiconductor material, and a step of removing a solvent.

Production method (d5): a step of dispersing a mixture of (1) a semiconductor material, (2) a surface modifier and (5) a group of modified compounds in (4) a polymerizable compound, and (4) a polymerizable compound. And a step of polymerizing the method.

Production method (d6): a step of dispersing a mixture of (1) a semiconductor material, (2) a surface modifier and (5) a group of modifiers in (3) a solvent in which (4-1) a polymer is dissolved And a step of removing the solvent.

The step of removing the solvent (3) included in the production methods (d2), (d4), and (d6) may be a step of allowing to stand at room temperature and naturally drying, or using a vacuum dryer. The drying may be performed under reduced pressure, or the step (3) of evaporating the solvent by heating may be performed.

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

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

For example, in the case of radical polymerization, a radical polymerization initiator is added to a mixture of (1) a semiconductor material, (2) a surface modifier, (4) a polymerizable compound, and (5) a modified group, The polymerization reaction can be promoted by generating radicals.

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

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

When (6) another surface modifier is used in the method 2 for producing a composition, it can be added together with (2) the surface modifier.

<< Composition Manufacturing Method 3 >>
Further, as the method for producing the composition of the present embodiment, the following production method (d7) can also be adopted.

Manufacturing method (d7): a manufacturing method including a step of melt-kneading (1) a semiconductor material, (2) a surface modifier, and (4-1) a polymer.

Production method (d8): (1) semiconductor material, (2) surface modifier, (4-1) polymer, (5A) step of melt-kneading raw material compound, and (4-1) polymer And a step of performing a modification treatment in a molten state.

Production method (d9): a step of producing a liquid composition containing (1) a semiconductor material and (2) a surface modifier, a step of extracting solid matter from the obtained liquid composition, and the obtained solid matter And a step of melt-kneading (4-1) the polymer.

Production method (d10): (1) a step of producing a liquid composition containing a semiconductor material, (2) a surface modifier, and (5) a group of modified substances, and taking out a solid content from the obtained liquid composition. A production method comprising the steps of: and a step of melt-kneading the obtained solid content and (4-1) polymer.

Production method (d11): a step of producing a liquid composition containing (1) a semiconductor material and (2) a surface modifier, a step of extracting solid matter from the obtained liquid composition, and the obtained solid matter And a step (5) of melt-kneading the modified product group and (4-1) the polymer.

In the melt-kneading step of the production methods (d7) to (d11), a mixture of the (4-1) polymer and another material may be melt-kneaded, and the melted (4-1) polymer may be mixed with other materials. Materials may be added. The "other material" refers to a material used in each production method in addition to (4-1) a polymer, and specifically, (1) a semiconductor material, (2) a surface modifier, (5A) a raw material compound, and (5) Refers to a group of modified substances.

The (5) modified product group added in the melt-kneading step of the production method (d11) can be obtained by modifying the starting compound (5A).

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

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

The above-mentioned production method (a1) or (a2) can be adopted in the step of producing the liquid composition of the production methods (d9) and (d11).

The above-mentioned production method (a3) or (a4) can be adopted in the step of producing the liquid composition of the production method (d10).

In the steps of taking out the solid content in the production methods (d9) to (d11), (3) the solvent and (4) the polymerizable compound constituting the liquid composition from the liquid composition by, for example, heating, decompression, air blowing and a combination thereof. By removing.

In the method 3 for producing a composition, when (6) another surface modifier is used, it can be added together with (2) the surface modifier.

<< Measurement of perovskite compounds >>
The amount of the perovskite compound contained in the composition of the present embodiment is determined by an inductively coupled plasma mass spectrometer ICP-MS (for example, PerkinElmer, ELAN DRCII), and an ion chromatograph (for example, Thermo Fisher Scientific Co., Ltd.). , Integration) can be used for the measurement.
The perovskite compound is dissolved in a good solvent such as N, N-dimethylformamide and then measured.
<< (5) Concentration measurement of Si element contained in modified body group >>
For the concentration (μg / g) of the Si element contained in the modified body group (5) contained in the composition of the present embodiment, an inductively coupled plasma mass spectrometer ICP-MS (for example, ELAN DRCII manufactured by PerkinElmer) is used. Use to measure.
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 the present embodiment is measured using an absolute PL quantum yield measuring device (for example, C9920-02 manufactured by Hamamatsu Photonics KK) under excitation light of 450 nm, room temperature, and the atmosphere.

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

<< Evaluation of heat resistance >>
The composition of the present embodiment is heated on a hot plate at 260 ° C. for 2 minutes, the quantum yield before and after heating is measured, and the retention rate is evaluated using the following formula.
Maintenance rate (%) = quantum yield after heat resistance test / quantum yield before heat resistance test × 100

The composition of the embodiment has a retention rate of 20% or more, 40% or more, 60% or more, or 80% or more in each of the above-described measurement methods. It may be present or may be 85% or more. Since the effect of heat resistance of the composition is high, the maintenance rate is preferably high.

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

The shape of the film is not particularly limited and may be any shape such as a sheet shape or a bar shape. In the present specification, the “bar-like shape” means, for example, a band-like shape in plan view extending in one direction. Examples of the band-like shape in plan view include a plate-like shape in which each side has a different length.

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

In the present specification, the thickness of the film refers to the front surface and the back surface in the thickness direction of the film when the side having the smallest value in the length, width and height of the film is defined as the “thickness direction”. Refers to the distance between. Specifically, the thickness of the film is measured at any three points on the film using a micrometer, and the average value of the measured values at the three points is taken as the film thickness.

The film may 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 for each layer.

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

Among the plurality of layers included in the laminated structure, examples of layers other than the above-mentioned films 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 a sheet shape and a bar shape.

(substrate)
The substrate is not particularly limited, but may be a film. The substrate is preferably light transmissive. A laminated structure including a substrate having a light-transmitting property is preferable because (1) it is easy to extract light emitted from the semiconductor material.

As a material for forming the substrate, for example, a polymer such as polyethylene terephthalate or a known material such as glass can be used.
For example, in the laminated structure, the above-mentioned film may be provided on the substrate.

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

One aspect of the present invention is a first substrate 20, a second substrate 21, a film 10 according to the present embodiment located between the first substrate 20 and the second substrate 21, and a sealing. A laminated structure having a layer 22 and the encapsulating layer 22 is disposed on a surface of the film 10 which is not in contact with the first substrate 20 and the second substrate 21. It is the structure 1a.

(Barrier layer)
The layer that the laminated structure according to the present embodiment may have is not particularly limited, and examples thereof include a barrier layer. A barrier layer may be included from the viewpoint of protecting the above-mentioned composition from water vapor in the outside air and air in the atmosphere.

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

(Light scattering layer)
The layer that the laminated structure according to the present embodiment may have is not particularly limited, and examples thereof include a light scattering layer. From the viewpoint of effectively utilizing the incident light, a light scattering layer may be included.
The light scattering layer is not particularly limited, but is preferably transparent from the viewpoint of extracting emitted light. As the light scattering layer, light scattering particles such as silica particles, or a known light scattering layer such as an amplification diffusion film can be used.

<< Light emitting device >>
The light emitting device according to this embodiment can be obtained by combining the film or laminated structure of this embodiment with a light source. The light-emitting device is a device that emits light by irradiating a film or a laminated structure provided in a light emission direction of the light source with light emitted from the light source so that the film or the laminated structure emits light.

Among the plurality of layers included in the laminated structure in the light emitting device, the layers other than the above-mentioned film, substrate, barrier layer, and light scattering layer include a light reflection member, a brightness enhancement portion, a prism sheet, a light guide plate, and a medium between elements Any layer such as a material layer may be used.

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

(light source)
As a light source that constitutes the light emitting device of this embodiment, (1) a light source that emits light included in the absorption wavelength band of the semiconductor material is used. For example, a light source having an emission wavelength of 600 nm or less is preferable from the viewpoint of emitting the semiconductor material in the film or the laminated structure described above. As the light source, for example, a known light source such as a light emitting diode (LED) such as a blue light emitting diode, a laser, or an EL can be used.

(Light reflection member)
The layer that may be included in the laminated structure forming the light emitting device of the present embodiment is not particularly limited, and examples thereof include a light reflecting member. A light emitting device having a light reflecting member can efficiently irradiate light from a light source toward a film or a laminated structure.

The light reflection member is not particularly limited, but may be a reflection film. As the reflecting film, for example, a known reflecting film such as a reflecting mirror, a film of reflecting particles, a reflecting metal film or a reflector can be used.

(Brightness enhancement section)
The layer that may be included in the laminated structure that configures the light emitting device of the present embodiment is not particularly limited, and examples thereof include a brightness enhancement portion. The brightness enhancement section may be included from the viewpoint of reflecting a part of the light back toward the direction in which the light is transmitted.

(Prism sheet)
The layer that may be included in the laminated structure that configures the light emitting device of the present embodiment is not particularly limited, but a prism sheet can be used. The prism sheet typically has a base material portion and a prism portion. The base material portion may be omitted depending on the adjacent member.

The prism sheet can be attached to an adjacent member via any appropriate adhesive layer (eg, adhesive layer, pressure-sensitive adhesive layer).

When the light emitting device is used in a display described later, the prism sheet is configured by arranging a plurality of unit prisms that are convex on the side opposite to the viewing side (back side). By arranging the convex portion of the prism sheet so as to face the back surface side, it becomes easy to collect light that passes through the prism sheet. Also, when the convex portion of the prism sheet is arranged facing the back side, compared to the case where the convex portion is arranged facing the viewing side, less light is reflected without entering the prism sheet, and a display with high brightness is displayed. Can be obtained.

(Light guide plate)
The layer that may be included in the laminated structure that configures the light emitting device of the present embodiment is not particularly limited, and examples thereof include a light guide plate. As the light guide plate, for example, a light guide plate having a lens pattern formed on the back side so that light from the lateral direction can be deflected in the thickness direction, a prism shape on either or both of the back side and the viewing side. Any appropriate light guide plate can be used, such as a light guide plate on which the above are formed.

(Medium material layer between elements)
The layer that may be included in the laminated structure that constitutes the light emitting device of the present embodiment is not particularly limited, but a layer composed of one or more medium materials (on the optical path between adjacent elements (layers) ( Media material layers between elements).

The one or more media contained in the media material layer between the elements include, but are not limited to, vacuum, air, gas, optical material, adhesive, optical adhesive, glass, polymer, solid, liquid, gel, cured. Materials, optical coupling materials, index matching or index mismatching materials, gradient index materials, cladding or anti-cladding materials, spacers, silica gel, brightness enhancing materials, scattering or diffusing materials, reflective or anti-reflective materials, wavelength selection Materials, wavelength selective anti-reflective materials, color filters, or suitable media known in the art.

Specific examples of the light emitting device of the present embodiment include those provided with a wavelength conversion material for EL displays and liquid crystal displays.
Specifically, the following respective structures (E1) to (E4) can be mentioned.

Configuration (E1): The composition of the present embodiment is put in a glass tube or the like and sealed, and the composition is arranged between the blue light emitting diode as a light source and the light guide plate so as to be along the end surface (side surface) of the light guide plate. Then, a backlight that converts blue light into green light or red light (on-edge backlight).

Configuration (E2): The composition of the present embodiment is formed into a sheet, and a film obtained by sandwiching the composition with two barrier films and sealing is placed on the light guide plate and placed on the end surface (side surface) of the light guide plate. A backlight (surface-mounted backlight) that converts blue light emitted from the blue light emitting diode to the sheet through a light guide plate into green light or red light.

Configuration (E3): A backlight (on-chip) that disperses the composition of the present embodiment in a resin or the like and installs it in the vicinity of a light emitting portion of a blue light emitting diode to convert the emitted blue light into green light or red light. Method backlight).

[Structure (E4): A backlight that disperses the composition of the present embodiment in a resist and installs it on a color filter to convert blue light emitted from a light source into green light or red light.

Further, as a specific example of the light emitting device according to the present embodiment, the composition of the present embodiment is molded and placed in the subsequent stage of the blue light emitting diode as a light source to convert blue light into green light or red light. Illumination that emits white light is included.

<< Display >>
As shown in FIG. 2, the display 3 of this embodiment includes a liquid crystal panel 40 and the above-described light emitting device 2 in this order from the viewing side. The light emitting device 2 includes a second stacked structure body 1b and a light source 30. In the second laminated structure 1b, the above-mentioned first laminated structure 1a further includes a prism sheet 50 and a light guide plate 60. The display may further comprise any suitable other member.

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

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

(Liquid crystal cell)
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, one substrate is provided with a color filter and a black matrix, and the other substrate is provided with a switching element for controlling electro-optical characteristics of liquid crystal and a scanning line for giving a gate signal to this switching element. And a signal line for supplying a source signal, a pixel electrode, and a counter electrode. The distance (cell gap) between the substrates can be controlled by a spacer or the like. An alignment film made of polyimide, for example, can be provided on the side of the substrate that is in contact with the liquid crystal layer.

(Polarizer)
The polarizing plate typically has a polarizer and protective layers disposed on both sides of the polarizer. The polarizer is typically an absorption-type polarizer.
Any appropriate polarizer is used as the polarizer. For example, a dichroic substance such as iodine or a dichroic dye is adsorbed on a hydrophilic polymer film such as a polyvinyl alcohol film, a partially formalized polyvinyl alcohol film, or an ethylene / vinyl acetate copolymer partially saponified film. Uniaxially stretched film, polyene oriented film such as polyvinyl alcohol dehydrated product, polyvinyl chloride dehydrochlorinated product and the like. Among these, a polarizer obtained by uniaxially stretching a polyvinyl alcohol film by adsorbing a dichroic substance such as iodine, has a high polarization dichroic ratio, and is particularly preferable.

<< Application of composition >>
The uses of the composition of the present embodiment include the following uses.

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

As the LED including the composition of the present embodiment, for example, the composition of the present embodiment and conductive particles such as ZnS are mixed and laminated in a film shape, the n-type transport layer is laminated on one surface, and the other surface is laminated on the other surface. Particles of (1) and (2), which have a structure in which a p-type transport layer is laminated and in which a hole of a p-type semiconductor and an electron of an n-type semiconductor are included in the composition of the junction surface by passing an electric current. Among them, there is a method of emitting light by canceling charges.

<Solar cell>
The composition of the present embodiment can be used as an electron transporting material contained in the active layer of a solar cell.

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

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

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

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

<Sensor>
The composition of the present embodiment is applied to a living body such as an image detection unit (image sensor) for a solid-state imaging device such as an X-ray imaging device and a CMOS image sensor, a fingerprint detection unit, a face detection unit, a vein detection unit and an iris detection unit. It can be used as a photoelectric conversion element (photodetection element) material included in a detection section for detecting a predetermined characteristic of a part or a detection section of an optical biosensor such as a pulse oximeter.

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

Manufacturing method (e1): A method for manufacturing a film, which includes a step of applying a liquid composition to obtain a coating film, and a step of (3) removing a solvent from the coating film.

Production method (e2): (4) a step of applying a liquid composition containing a polymerizable compound to obtain a coating film, and a step of polymerizing the (4) polymerizable compound contained in the obtained coating film. A method of manufacturing a film including.

Production method (e3): A method for producing a film by molding the composition obtained by the above-mentioned production methods (d1) to (d6).

The film produced by the above production methods (e1) and (e2) may be peeled off from the production position and used.

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

Production method (f1): Lamination including a step of producing a liquid composition, a step of applying the obtained liquid composition onto a substrate, and a step of removing (3) a solvent from the obtained coating film Structure manufacturing method.

Manufacturing method (f2): A manufacturing method of a laminated structure including a step of attaching a film to a substrate.

Production method (f3): (4) A step of producing a liquid composition containing a polymerizable compound, a step of applying the obtained liquid composition on a substrate, and a step of applying the obtained coating film (4) And a step of polymerizing the polymerizable compound.

The above-mentioned manufacturing methods (c1) to (c5) can be adopted in the steps of manufacturing the liquid composition in the manufacturing methods (f1) and (f3).

The step of applying the liquid composition on the substrate in the production methods (f1) and (f3) is not particularly limited, but is a gravure coating method, a bar coating method, a printing method, a spray method, a spin coating method, a dip method, Known coating and coating methods such as a die coating method can be used.

The step of removing the solvent (3) in the production method (f1) may be the same step as the step of removing the solvent (3) included in the production methods (d2), (d4), and (d6) described above. it can.

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

In the step of bonding the film to the substrate in the manufacturing method (f2), any adhesive can be used.

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

The method for producing a laminated structure may further include a step of laminating an arbitrary film on the obtained laminated structure.

As an arbitrary film to be laminated, for example, a reflection film or a diffusion film can be mentioned.

Arbitrary adhesives can be used in the process of laminating the films.

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 including the above-mentioned light source and a step of installing the above-mentioned film or laminated structure on the optical path of light emitted from the light source can be mentioned.

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

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

(Measurement of N content contained in amine compound)
X-ray photoelectron spectroscopy (XPS) of the compositions obtained in Examples 1 to 3 (Quantera SXM, manufactured by ULVAC-PHI Co., Ltd., AlKα photoelectron take-off angle of 45 degrees, aperture diameter of 100 μm, C 1s of surface contaminated hydrocarbons. The peak attributed to is used as a reference for charge correction with 284.6 eV), and the ratio (N / Pb (molar ratio)) of the moles of Pb in the perovskite and the moles of N in the amine compound contained in the composition was measured. ) Was calculated. XPS measurement was performed after casting 0.05 mL of a composition containing perovskite on a glass substrate of 1 cm × 1 cm and drying.

(Measurement of concentration of perovskite compound)
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, a dispersion liquid was obtained by redispersing (1) the semiconductor material obtained by the method described below in toluene that was precisely weighed. Then, the perovskite compound was dissolved in the obtained dispersion by adding N, N-dimethylformamide.

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

(Measurement of quantum yield)
The quantum yields of the compositions obtained in Examples 1 to 3 and Comparative Example 1 were measured by using an absolute PL quantum yield measuring device (C9920-02, manufactured by Hamamatsu Photonics Co., Ltd.), excitation light 450 nm, room temperature, It was measured under the atmosphere.

(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 retention rate was calculated using the following formula. It can be evaluated that the higher the maintenance rate thus obtained is, the higher the heat resistance is.
Maintenance rate (%) = quantum yield after heat resistance test / quantum yield before heat resistance test × 100

((1) Observation of semiconductor material by transmission electron microscope)
(1) The semiconductor material was observed using a transmission electron microscope (JEM-2200FS manufactured by JEOL Ltd.). The sample for observation was obtained by collecting (1) a semiconductor material from the composition on a grid with a supporting film. The observation conditions were an acceleration voltage of 200 kV.

The distance between the parallel lines when the image of the semiconductor material shown in the obtained electron micrograph was sandwiched by two parallel lines was calculated as the Feret diameter. The arithmetic average value of the Feret diameters of 20 semiconductor materials was obtained, and the average Feret diameter was obtained.

(Calculation of the molar ratio [Si / B] between the B component of the perovskite compound and the Si element of the modified body) The substance amount (B) (unit: mol) of the metal ion, which is the B component of the perovskite compound, is calculated by inductive coupling. The mass of the metal as the component B was measured by plasma mass spectrometry (ICP-MS), and the measured value was converted into the amount of the substance to obtain the value.

The substance amount (Si) of the Si element of the reformer is calculated from the value obtained by converting the mass of the raw material compound of the reformer used into the substance amount and the Si amount (substance amount) contained in the unit mass of the raw material compound. It was 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] was calculated from the substance amount (Si) of the Si element and the substance amount (B) of the metal ion that is the B component of the perovskite compound.

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

0.276 g of lead bromide (PbBr ₂ ) was mixed with 20 mL of 1-octadecene solvent. After stirring with a magnetic stirrer and heating at 120 ° C. for 1 hour while flowing nitrogen, 2 mL of oleic acid and 2.117 mL of N, N-dimethyl-n-octadecylamine were added to prepare a lead bromide dispersion. Prepared.

After heating the lead bromide dispersion to a temperature of 130 ° C., 1.6 mL of the above cesium carbonate solution was added. After the addition, the reaction vessel was soaked in ice water to lower the temperature to room temperature to obtain a dispersion liquid.

Then, the dispersion was centrifuged at 10,000 rpm for 5 minutes to separate the precipitate, and then 15 mL of ethyl acetate and 5 mL of toluene were added to disperse the dispersion, and then the dispersion was centrifuged again at 10,000 rpm for 5 minutes to separate the precipitate. Washed. After washing three times, a precipitate perovskite compound was obtained. After the perovskite compound was dispersed in 10 mL of toluene, 0.5 mL was again collected and dispersed in 4.5 mL of toluene to obtain a dispersion liquid containing the perovskite compound and the solvent.

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

When the X-ray diffraction pattern of the compound recovered by naturally drying the solvent was measured by an X-ray diffraction measurement device (XRD, Cu Kα ray, X'pert PRO MPD, Spectris Co., Ltd.), it was found at the position of 2θ = 14 ° ( It has a peak derived from hkl) = (001) and was confirmed to have a three-dimensional perovskite type crystal structure.

Next, 100 μL of organopolysilazane (Durazane 1500 Slow Cure, manufactured by Merck Performance Materials, Inc .: 0.967 g / cm ³ ) was mixed with the above-mentioned 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 was Si / Pb = 172.

-The above dispersion liquid was subjected to a modification treatment for 1 day while stirring with a stirrer at a humidity condition of 25 ° C and 80%.

50 μL of the dispersion liquid after the above modification treatment was cast on a glass substrate of 1 cm × 1 cm size, naturally dried, and then baked at 100 ° C. for 12 hours to obtain a composition. When the maintenance rate was calculated by measuring the quantum yield before and after the heat resistance test, the maintenance rate was 42.7%. The results are shown in Table 1.

[Example 2]
By the same method as in Example 1, a dispersion liquid containing a perovskite compound and N, N-dimethyl-n-octadecylamine was obtained.
Next, 100 μL of organopolysilazane (Durazane 1500 Rapid Cure, manufactured by Merck Performance Materials, Inc .: 0.967 g / cm ³ ) was mixed with the above-mentioned 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 was Si / Pb = 50.4.

50 μL of the dispersion liquid after the above modification treatment was cast on a glass substrate of 1 cm × 1 cm size, naturally dried, and then baked at 100 ° C. for 12 hours to obtain a composition. When the maintenance rate was calculated by measuring the quantum yield before and after the durability test, the maintenance rate was 86.4%. The results are shown in Table 1.

[Example 3]
A composition was obtained in the same manner as in Example 2 except that the addition amount of organopolysilazane (Durazane 1500 Rapid Cure, manufactured by Merck Performance Materials, Inc .: 0.967 g / cm ³ ) was 300 μL. The molar ratio of the Si element contained in the organopolysilazane and the Pb element contained in the perovskite compound in the dispersion was Si / Pb = 151.

50 μL of the above dispersion liquid was cast on a glass substrate of 1 cm × 1 cm size, naturally dried, and then baked at 100 ° C. for 12 hours to obtain a composition. When the maintenance rate was calculated by measuring the quantum yield before and after the heat resistance test, the maintenance rate was 77.9%. The results are shown in Table 1.

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

0.276 g of lead bromide (PbBr ₂ ) was mixed with 20 mL of 1-octadecene 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 liquid.

After raising the temperature of the lead bromide dispersion to 160 ° C., 1.6 mL of the above cesium carbonate solution was added. After the addition, the reaction vessel was soaked in ice water to lower the temperature to room temperature to obtain a dispersion liquid.

Next, the dispersion was centrifuged at 10,000 rpm for 5 minutes to obtain a perovskite compound as a precipitate. After dispersing the perovskite compound in 5 mL of toluene, 0.5 mL was again collected and dispersed in 4.5 mL of toluene to obtain a dispersion liquid 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 average ferret diameter of the perovskite compound observed by TEM was 11 nm.

After diluting with toluene so that the concentration of the perovskite compound was 200 ppm (μg / g), the quantum yield measured by a quantum yield measuring device was 30%.
Next, 100 μL of organopolysilazane (Durazane 1500 Slow Cure, manufactured by Merck Performance Materials, Inc .: 0.967 g / cm ³ ) was mixed with Dispersion Liquid 1 containing the above-mentioned perovskite compound and a 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 was Si / Pb = 76.

50 μL of the dispersion liquid after the above modification treatment was cast on a glass substrate of 1 cm × 1 cm size, naturally dried, and then baked at 100 ° C. for 12 hours to obtain a composition. When the maintenance rate was calculated by measuring the quantum yield before and after the heat resistance test, the maintenance rate was 8%. The results are shown in Table 1.

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

[Reference Example 1]
The composition described in Examples 1 to 3 is put in a glass tube or the like and sealed, and then the composition is placed between a blue light emitting diode which is a light source and a light guide plate, whereby blue light of the blue light emitting diode is emitted. Manufacture backlights that can be converted into green and red light.

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

[Reference Example 3]
By installing the compositions described in Examples 1 to 3 in the vicinity of the light emitting portion of a blue light emitting diode, a backlight capable of converting the emitted blue light into green light or red light is manufactured.

[Reference Example 4]
The wavelength conversion material can be obtained by mixing the composition described in Examples 1 to 3 and the resist and then removing the solvent. By arranging the obtained wavelength conversion material between the blue light emitting diode which is the light source and the light guide plate or in the subsequent stage of the OLED which is the light source, a backlight capable of converting the blue light of the light source into green light or red light is provided. To manufacture.

[Reference Example 5]
The composition described in Examples 1 to 3 is mixed with conductive particles such as ZnS to form a film, an n-type transport layer is laminated on one side, and a p-type transport layer is laminated on the other side to obtain an LED. . When a current is passed, holes in the p-type semiconductor and electrons in the n-type semiconductor cancel out the charges in the perovskite compound on the junction surface, so that light can be emitted.

[Reference Example 6]
A titanium oxide dense layer is laminated on the surface of a fluorine-doped tin oxide (FTO) substrate, a porous aluminum oxide layer is laminated thereon, and the composition described in Examples 1 to 3 is laminated thereon. After removing the solvent, holes such as 2,2 '-, 7,7'-tetrakis- (N, N'-di-p-methoxyphenylamine) -9,9'-spirobifluorene (Spiro-OMeTAD) are removed from above. A transport layer is laminated, and a silver (Ag) layer is laminated on it to prepare a solar cell.

[Reference Example 7]
The composition of the present embodiment can be obtained by removing the solvent of the compositions described in Examples 1 to 3 and molding. By placing this composition in the subsequent stage of the blue light emitting diode, the composition of the blue light emitting diode can be obtained. We manufacture laser diode lighting that emits white light by converting the blue light that illuminates an object into green light and red light.

[Reference Example 8]
The composition of this embodiment can be obtained by removing the solvent of the composition described in Examples 1 to 3 and molding. By using the obtained composition as a part of a photoelectric conversion layer, a photoelectric conversion element (photodetection element) material used for a detection unit that detects light is manufactured. The photoelectric conversion element material is used for a part of a living body such as an image detection part (image sensor) for a solid-state imaging device such as an X-ray imaging device and a CMOS image sensor, a fingerprint detection part, a face detection part, a vein detection part and an iris detection part. It is used in optical biosensors such as pulse oximeters that detect specific characteristics.

According to the present invention, there are provided a composition having high heat resistance including a light emitting semiconductor material, a film using the composition, a laminated structure using the film, a light emitting device and a display including the laminated structure. It becomes possible.
Therefore, the composition of the present invention, the film using the composition, the laminated structure using the film, the light emitting device and the display including the laminated structure can be suitably used for light emitting applications.

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

Claims

A composition comprising the component (1) and the component (2).
(1) Component: Luminescent semiconductor material (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
The composition according to claim 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 a hexahedron centered on B in the perovskite type crystal structure, and is a monovalent cation.
X represents a component located at each vertex of the octahedron centered on B in the perovskite type crystal structure, and is at least one anion selected from the group consisting of a halide ion and a thiocyanate ion.
In the perovskite type crystal structure, B is a component located at the center of the hexahedron having A at its apex and the octahedron having X at its apex, and is a metal ion. )
The composition according to claim 1 or 2, further comprising (5) component.
Component (5): silazane, silazane modified product, compound represented by the following formula (C1), modified product of compound represented by the following formula (C1), compound represented by the following formula (C2), below A modified product of the compound represented by formula (C2), a compound represented by the following formula (A5-51), a modified product of the compound represented by the following formula (A5-51), and a compound represented by the following formula (A5-52) ), One or more compounds selected from the group consisting of a compound represented by the following formula (A5-52), a modified product of sodium silicate, and a modified product of sodium silicate.

(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 are each independently 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. It represents up to 20 unsaturated hydrocarbon groups.
When Y 5 is a single bond or a sulfur atom, R 30 is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, or an unsaturated hydrocarbon group having 2 to 20 carbon atoms. R 31 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, or an unsaturated hydrocarbon group having 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 a carbon atom having 3 to 30 carbon atoms. It represents 2 to 20 unsaturated hydrocarbon groups.
In formula (C1) and formula (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.
a is an integer of 1 to 3.
When a is 2 or 3, a plurality of Y 5 s may be the same or different.
When a is 2 or 3, a plurality of R 30's may be the same or different.
When a is 2 or 3, a plurality of R 32's may be the same or different.
When a is 1 or 2, a plurality of R 31's may be the same or different. )

(In formulas (A5-51) and (A5-52), A C represents a divalent hydrocarbon group, and Y 15 represents an oxygen atom or a sulfur atom.
R 122 and R 123 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a cycloalkyl group having 3 to 30 carbon atoms, and R 124 is an alkyl group having 1 to 20 carbon atoms. Or a cycloalkyl group having 3 to 30 carbon atoms, R 125 and R 126 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, Alternatively, it represents a cycloalkyl group having 3 to 30 carbon atoms.
The hydrogen atoms contained in the alkyl group and cycloalkyl group represented by R 122 to R 126 may be each independently substituted with a halogen atom or an amino group. )
The composition according to any one of claims 1 to 3, further comprising at least one selected from the group consisting of component (3), component (4), and component (4-1).
(3) component: solvent (4) component: polymerizable compound (4-1) component: polymer
A film comprising the composition according to any one of claims 1 to 4 as a forming material.
A laminated structure including the film according to claim 5.
A light emitting device comprising the laminated structure according to claim 6.
A display provided with the laminated structure according to claim 6.