WO2018117130A1

WO2018117130A1 - Composition, film, laminated structure, light-emitting device, display, and method for producing composition

Info

Publication number: WO2018117130A1
Application number: PCT/JP2017/045618
Authority: WO
Inventors: 翔太内藤; 酒谷　能彰
Original assignee: 住友化学株式会社
Priority date: 2016-12-22
Filing date: 2017-12-20
Publication date: 2018-06-28
Also published as: JPWO2018117130A1; CN110088230A; CN115521774A; JP6830964B2; TW201840670A

Abstract

The present invention relates to a light-emitting composition comprising (1), (2), and (3). Said (1) consists of semiconductor particles, (2) is an organic compound including an amino group, an alkoxy group, and a silicon atom, and (3) is at least one type selected from the group consisting of polymerizable compounds and polymers. Said (1) preferably consists of particles of a perovskite compound comprising A, B, and X as constituent components. Said A is a component located at each apex of a hexahedron centered about B in the perovskite-type crystal structure, and is a monovalent positive ion. X represents a component located at each apex of an octahedron centered about B in the perovskite-type crystal structure, and is at least one type of negative ion selected from the group consisting of halide ions and a thiocyanate ion. B is a metallic ion.

Description

COMPOSITION, FILM, LAMINATED STRUCTURE, LIGHT EMITTING DEVICE, DISPLAY, AND METHOD FOR PRODUCING COMPOSITION

The present invention relates to a composition, a film, a laminated structure, a light emitting device, a display, and a method for producing the composition.
This application claims priority based on Japanese Patent Application No. 2016-250174 for which it applied to Japan on December 22, 2016, and uses the content here.

In recent years, interest in the luminescent properties of semiconductor materials has increased.
For example, a composition having strong emission intensity in the range of the ultraviolet to red spectral region under room temperature conditions has been reported (Non-Patent Document 1).

However, when the composition described in Non-Patent Document 1 is used as a light emitting material, further improvement in thermal durability is required.
This invention is made | formed in view of the said subject, Comprising: It is providing the manufacturing method of a composition, a film, a laminated structure, a light-emitting device, a display, and a composition with high heat durability containing a semiconductor fine particle. Objective.

In order to solve the above-mentioned problems, the present inventors have intensively studied, and as a result, have reached the following present invention.

That is, the present invention includes the following [1] to [11].
[1] A composition having luminescent properties, comprising (1), (2), and (3).
(1) Semiconductor fine particles (2) Organic compound having an amino group, an alkoxy group, and a silicon atom (3) At least one selected from the group consisting of a polymerizable compound and a polymer [2] The above (1) is A The composition according to [1], wherein the composition is a fine particle of a perovskite compound having, B, and X as constituent components.
A is a component located at each vertex of a hexahedron centered on B in the perovskite crystal structure, and is a monovalent cation.
X represents a component located at each vertex of an octahedron centered on B in the perovskite crystal structure, and is one or more anions selected from the group consisting of halide ions and thiocyanate ions.
B is a component located at the center of a hexahedron that arranges A at the apex and an octahedron that arranges X at the apex in the perovskite crystal structure, and is a metal ion.
[3] The composition according to [1] or [2], wherein (1) is a mixture of the dispersion dispersed in (3) and (2).
[4] The composition according to any one of [1] to [3], further comprising (4) at least one selected from the group consisting of (4) ammonia, amine, carboxylic acid, and salts or ions thereof. object.
[5] A composition comprising (1), (2) and (3 ′), wherein the total content of (1), (2) and (3 ′) is relative to the total mass of the composition The composition which is 90 mass% or more.
(1) Semiconductor fine particles (2) Organic compound having amino group, alkoxy group, and silicon atom (3 ′) Polymer [6] Further, (4) From ammonia, amine, carboxylic acid, and salts or ions thereof The composition according to the above [5], comprising at least one selected from the group consisting of:
[7] A film comprising the composition according to [5] or [6].
[8] A laminated structure having a plurality of layers, at least one of which is a layer made of the composition according to [5] or [6].
[9] A light emitting device including the laminated structure according to [8].
[10] A display comprising the laminated structure according to [8].
[11] A step of dispersing (1) in (3) to obtain a dispersion;
The manufacturing method of the composition which has luminescent property including the process of mixing the obtained dispersion and (2).
(1) Semiconductor fine particles (2) Organic compounds having amino groups, alkoxy groups, and silicon atoms (3) At least one selected from the group consisting of polymerizable compounds and polymers

According to the present invention, it is possible to provide a composition, a film, a laminated structure, a light-emitting device, a display, and a method for producing the composition having high thermal durability including semiconductor fine particles.

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. It is a graph which shows the result of the thermal durability on 60 degreeC conditions of the composition based on this invention acquired in the Example.

Hereinafter, embodiments of the present invention will be described in detail.
<Composition>
The composition of the present invention has luminescent properties. “Luminescent” refers to the property of emitting light. The light emitting property is preferably a property of emitting light by excitation of electrons, and more preferably a property of emitting light by excitation of electrons by excitation light. The wavelength of the excitation light may be, for example, 200 nm to 800 nm, 250 nm to 700 nm, or 300 nm to 600 nm.

The composition of the present invention comprises (1), (2), and (3).
(1) Semiconductor fine particles (2) Organic compounds having amino groups, alkoxy groups, and silicon atoms (3) At least one selected from the group consisting of polymerizable compounds and polymers

The composition may further include (4) at least one selected from the group consisting of (4) ammonia, amines, and carboxylic acids, and salts or ions thereof.
Further, it may have other components other than (1) to (4).
Examples of other components include a compound having an amorphous structure composed of some impurities and elemental components constituting semiconductor fine particles, a polymerization initiator, and a solvent.
The content of other components is preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 1% by mass or less with respect to the total mass of the composition.

As a result of intensive studies by the inventors,
In a composition comprising (1) semiconductor fine particles, (2) an organic compound having an amino group, an alkoxy group, and a silicon atom, and (3) a polymerizable compound and at least one selected from the group consisting of polymers. It was found that the property can be improved.
This is because the organic compound (2) prevents the electrons trapped in the defects on the surface of the semiconductor fine particles (1) from being deactivated, and the organic compound (2) is strongly adsorbed. Therefore, it is considered that the heat durability is improved by being difficult to come off due to the influence of heat.
In the composition of this embodiment, the total content of (1), (2), and (3) including (1), (2), and (3) is 90 mass with respect to the total mass of the composition. % Or more, 95 mass% or more, 99 mass% or more, or 100 mass%.

The composition of the present invention includes (1), (2), and (3 ′), and the total content of (1), (2), and (3 ′) is 90 with respect to the total mass of the composition. The composition which is the mass% or more may be sufficient.
(1) Semiconductor fine particles (2) Organic compound having amino group, alkoxy group, and silicon atom (3 ′) polymer

In the composition of the present embodiment, the total content of (1), (2) and (3 ′) may be 95% by mass or more with respect to the total mass of the composition, and is 99% by mass or more. It may be 100 mass%.
The composition may further contain (4) at least one selected from the group consisting of (4) ammonia, amines, and carboxylic acids, and salts or ions thereof. Components other than (1), (2), (3 ′), and (4) include the same components as the other components described above.

In the composition of this embodiment including (1), (2), and (3), the content of (1) with respect to the total mass of the composition is not particularly limited, but the semiconductor fine particles are condensed. From the viewpoint of making it difficult and preventing concentration quenching, it is preferably 50% by mass or less, more preferably 1% by mass or less, further preferably 0.5% by mass or less, and good. From the viewpoint of obtaining the quantum yield, it is preferably 0.0001% by mass or more, more preferably 0.0005% by mass or more, and further preferably 0.001% by mass or more.
The above upper limit value and lower limit value can be arbitrarily combined.
The content of (1) with respect to the total mass of the composition is usually 0.0001 to 50% by mass.
The content of (1) with respect to the total mass of the composition is preferably 0.0001 to 1% by mass, more preferably 0.0005 to 1% by mass, and 0.001 to 0.5% by mass. More preferably.
The composition in which the range related to the blending of (1) is within the above range is preferable in that the aggregation of the semiconductor fine particles of (1) hardly occurs and the light emitting property is also satisfactorily exhibited.
In the present specification, the content of the semiconductor fine particles of (1) with respect to the total mass of the composition can be measured by, for example, an inductively coupled plasma mass spectrometer (hereinafter also referred to as ICP-MS) and an ion chromatograph. it can.

In the composition of this embodiment including (1), (2), and (3), the total content of (1) and (2) with respect to the total mass of the composition is not particularly limited, From the viewpoint of making the semiconductor fine particles difficult to condense and preventing concentration quenching, it is preferably 60% by mass or less, more preferably 10% by mass or less, and further preferably 2% by mass or less. It is particularly preferred that the amount be 0.5 mass% or less, and from the viewpoint of obtaining a good quantum yield, it is preferably 0.0002 mass% or more, more preferably 0.002 mass% or more, More preferably, it is 0.005 mass% or more.
The above upper limit value and lower limit value can be arbitrarily combined.
The total content of (1) and (2) with respect to the total mass of the composition is usually 0.0002 to 60% by mass.
The total content of (1) and (2) with respect to the total mass of the composition is preferably 0.001 to 10% by mass, more preferably 0.002 to 2% by mass, and 0.005 to More preferably, it is 0.6 mass%.
The composition in which the range related to the blending ratio of (1) and (2) is within the above range is preferable in that the aggregation of the semiconductor fine particles of (1) hardly occurs and the light emission property is also exhibited well.

In the composition of this embodiment including (1), (2), and (3 ′), the content of (1) with respect to the total volume of the composition is not particularly limited, but the semiconductor fine particles are condensed. From the viewpoint of making it difficult to prevent the concentration quenching, it is preferably 100 g / L or less, more preferably 10 g / L or less, further preferably 5 g / L or less, and good quantum From the viewpoint of obtaining a yield, it is preferably 0.01 g / L or more, more preferably 0.1 g / L or more, and further preferably 0.5 g / L or more.
The above upper limit value and lower limit value can be arbitrarily combined.
The content of (1) with respect to the total volume of the composition is preferably 0.01 to 100 g / L, more preferably 0.1 to 10 g / L, and 0.5 to 5 g / L. More preferably.
The composition in which the range related to the blending of (1) is within the above range is preferable in that the light emitting property is satisfactorily exhibited.
In the present specification, the content of (1) relative to the total volume of the composition can be measured by, for example, ICP-MS and ion chromatograph.
When the composition is in the form of a film, the total volume of the composition can be calculated by cutting the film into 1 cm in length and 1 cm in width and measuring the thickness with a micrometer or the like.
When the composition is a liquid, the total volume of the composition can be measured using a graduated cylinder.
When the composition is a powder, the total volume of the composition is based on JIS R 93-1-2-3: 1999, the heavy bulk specific gravity is measured, and the weight of the composition used for the measurement is the weight of the heavy bulk It can be calculated by dividing by specific gravity.

In the composition of this embodiment including (1), (2), and (3 ′), the total content of (1) and (2) with respect to the total volume of the composition is not particularly limited. From the viewpoint of making the semiconductor fine particles difficult to condense and from the viewpoint of preventing concentration quenching, it is preferably 1000 g / L or less, more preferably 500 g / L or less, and even more preferably 300 g / L or less, Moreover, from a viewpoint of obtaining a favorable quantum yield, it is preferably 0.02 g / L or more, more preferably 0.2 g / L or more, and further preferably 0.6 g / L or more.
The above upper limit value and lower limit value can be arbitrarily combined.
The total content of (1) and (2) with respect to the total volume of the composition is preferably 0.02 to 1000 g / L, more preferably 0.2 to 500 g / L, and more preferably 0.6 to More preferably, it is 300 g / L.
A composition in which the range relating to the blending ratio of (1) and (2) is within the above range is preferable in that the light emitting property is exhibited well.

Hereinafter, embodiments of the composition of the present invention will be described.

(1) Semiconductor fine particles The composition according to the present invention preferably includes (1) semiconductor fine particles, and (1) the semiconductor fine particles are dispersed. Examples of the dispersion medium include (3) at least one selected from the group consisting of a polymerizable compound and a polymer, and (3 ′) a polymer.
As used herein, “dispersed” refers to a state in which semiconductor fine particles are suspended or suspended in a dispersion medium.
Examples of the semiconductor fine particles of the present invention include Group II-VI compound semiconductor crystal fine particles, Group II-V compound semiconductor crystal fine particles, Group III-V compound semiconductor crystal fine particles, and Group III-IV. Group compound semiconductor crystal particles, Group III-VI compound semiconductor crystal particles, Group IV-VI compound semiconductor crystal particles, Transition metal-p-block compound semiconductor crystal particles, and Perovskite compound particles Etc.
From the viewpoint of obtaining a good quantum yield, the semiconductor fine particles are preferably semiconductor crystal fine particles containing cadmium, semiconductor crystal fine particles containing indium, and perovskite compound fine particles, and particle size control is not required so strictly. From the viewpoint of easily obtaining a light emission peak with a narrow half-value width, fine particles of a perovskite compound are more preferable.
At least a part of these semiconductor fine particles may be coated with (2) an organic compound having an amino group, an alkoxy group, and a silicon atom.

The average particle size of the semiconductor fine particles contained in the composition is not particularly limited, but from the viewpoint of maintaining a good crystal structure, the average particle size is preferably 1 nm or more, and 2 nm or more. Is more preferably 3 nm or more, and from the viewpoint of making it difficult for the semiconductor fine particles according to the present invention to settle, the average particle diameter is preferably 10 μm or less, more preferably 1 μm or less, More preferably, it is 500 nm or less.
The above upper limit value and lower limit value can be arbitrarily combined.
The average particle diameter of the semiconductor fine particles contained in the composition is not particularly limited, but the average particle diameter is 1 nm or more and 10 μm from the viewpoint of making the semiconductor fine particles difficult to settle and maintaining a good crystal structure. Is preferably 2 nm or more and 1 μm or less, and more preferably 3 nm or more and 500 nm or less.
In this specification, the average particle diameter of the semiconductor fine particles contained in the composition 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, by observing the maximum ferret diameter of 20 semiconductor fine particles contained in the composition by TEM or SEM, and calculating the average maximum ferret diameter which is an average value thereof, The diameter can be determined. In this specification, the “maximum ferret diameter” means the maximum distance between two parallel straight lines sandwiching semiconductor fine particles on a TEM or SEM image.

The particle size distribution of the semiconductor fine particles contained in the composition is not particularly limited, but the median diameter (D50) is preferably 3 nm or more, preferably 4 nm or more, from the viewpoint of maintaining a good crystal structure. More preferably, it is more preferably 5 nm or more, and from the viewpoint of making it difficult for the semiconductor fine particles according to the present invention to settle, the median diameter (D50) is preferably 5 μm or less, and preferably 500 nm or less. More preferably, it is 100 nm or less.
As another aspect of this embodiment, the median diameter (D50) in the particle size distribution of the semiconductor fine particles contained in the composition is preferably 3 nm to 5 μm, more preferably 4 nm to 500 nm, and more preferably 5 nm to 100 nm. More preferably.
In this specification, the particle size distribution of the semiconductor fine particles contained in the composition can be measured by, for example, TEM or SEM. Specifically, the maximum ferret diameter of 20 semiconductor fine particles contained in the composition is observed by TEM or SEM, and the median diameter (D50) can be obtained from their distribution.

(Group II-VI compound semiconductor crystal fine particles)
The group II-VI compound semiconductor includes a group 2 or group 12 element and a group 16 element of the periodic table.
In the present specification, “periodic table” means a long-period type periodic table.
Examples of binary Group II-VI compound semiconductors include CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, HgS, HgSe, and HgTe.
Examples of binary group II-VI group compound semiconductors containing an element selected from group 2 of the periodic table (first element) and an element selected from group 16 of the periodic table (second element) include: MgS, MgSe, MgTe, CaS, CaSe, CaTe, SrS, SrSe, SrTe, BaS, BaSe, or BaTe can be mentioned.
A Group II-VI compound semiconductor containing an element selected from Group 2 of the periodic table (first element) and an element selected from Group 16 of the periodic table (second element) is selected from Group 2 of the periodic table It may be a ternary group II-VI compound semiconductor containing one kind of element (first element) and two kinds of elements (second elements) selected from group 16 of the periodic table, or a periodic table A ternary Group II-VI compound semiconductor comprising two types of elements selected from Group 2 (first element) and one type of element selected from Group 16 of the periodic table (second element). Alternatively, a quaternary group II-VI containing two types of elements (first element) selected from group 2 of the periodic table and two types of elements (second element) selected from group 16 of the periodic table It may be a group compound semiconductor.

Examples of binary group II-VI compound semiconductors that include an element selected from group 12 of the periodic table (first element) and an element selected from group 16 of the periodic table (second element) include: ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, HgS, HgSe, or HgTe can be mentioned.
A Group II-VI compound semiconductor containing an element selected from Group 12 of the periodic table (first element) and an element selected from Group 16 of the periodic table (second element) is selected from Group 12 of the periodic table It may be a ternary group II-VI compound semiconductor containing one kind of element (first element) and two kinds of elements (second elements) selected from group 16 of the periodic table, or a periodic table A ternary Group II-VI compound semiconductor comprising two types of elements selected from Group 12 (first element) and one type of element selected from Group 16 of the periodic table (second element). Alternatively, a quaternary group II-VI containing two types of elements selected from group 12 of the periodic table (first element) and two types of elements selected from group 16 of the periodic table (second element) It may be a group compound semiconductor.
The Group II-VI compound semiconductor may contain an element other than Groups 2, 12, and 16 of the periodic table as a doping element.

(Group II-V compound semiconductor crystal fine particles)
The group II-group V compound semiconductor includes a group 12 element and a group 15 element of the periodic table.
Examples of binary group II-V compound semiconductors containing an element selected from group 12 of the periodic table (first element) and an element selected from group 15 of the periodic table (second element) include: Zn ₃ P ₂ , Zn ₃ As ₂ , Cd ₃ P ₂ , Cd ₃ As ₂ , Cd ₃ N ₂ , or Zn ₃ N ₂ may be mentioned.
A Group II-V compound semiconductor including an element selected from Group 12 of the periodic table (first element) and an element selected from Group 15 of the periodic table (second element) is selected from Group 12 of the periodic table. It may be a ternary group II-V compound semiconductor containing one type of element (first element) and two types of elements (second element) selected from group 15 of the periodic table, or a periodic table A ternary Group II-V compound semiconductor comprising two elements selected from Group 12 (first element) and one element selected from Group 15 of the periodic table (second element). Alternatively, a quaternary group II-V containing two types of elements (first elements) selected from group 12 of the periodic table and two types of elements (second elements) selected from group 15 of the periodic table It may be a group compound semiconductor. The Group II-V compound semiconductor may contain an element other than Groups 12 and 15 of the periodic table as a doping element.

(Group III-V compound semiconductor crystal fine particles)
The Group III-V compound semiconductor includes an element selected from Group 13 of the periodic table and an element selected from Group 15. As a binary group III-V compound semiconductor containing an element selected from group 13 of the periodic table (first element) and an element selected from group 15 of the periodic table (second element), for example, BP AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs, InSb, AlN, or BN.
A Group III-V compound semiconductor containing an element selected from Group 13 of the periodic table (first element) and an element selected from Group 15 of the periodic table (second element) is selected from Group 13 of the periodic table. It may be a ternary Group III-V compound semiconductor containing one type of element (first element) and two types of elements (second element) selected from Group 15 of the periodic table, or a periodic table A ternary Group III-V compound semiconductor comprising two types of elements selected from Group 13 (first element) and one type of element selected from Group 15 of the periodic table (second element). Alternatively, a quaternary group III-V containing two types of elements (first elements) selected from group 13 of the periodic table and two types of elements (second elements) selected from group 15 of the periodic table It may be a group compound semiconductor.
The Group III-V compound semiconductor may contain an element other than Groups 13 and 15 of the periodic table as a doping element.

(Group III-IV compound semiconductor crystal fine particles)
The group III-IV compound semiconductor includes an element selected from group 13 of the periodic table and an element selected from group 14. Examples of binary group III-IV compound semiconductors containing an element selected from group 13 of the periodic table (first element) and an element selected from group 14 of the periodic table (second element) include B _{_{_{_{4 C 3, Al 4 C 3}}}} , Ga 4 C 3 and the like.
A group III-IV compound semiconductor including an element selected from group 13 of the periodic table (first element) and an element selected from group 14 of the periodic table (second element) is selected from group 13 of the periodic table. It may be a ternary group III-IV compound semiconductor containing one type of element (first element) and two types of elements (second element) selected from group 14 of the periodic table, or a periodic table A ternary group III-IV compound semiconductor comprising two elements selected from group 13 (first element) and one element (second element) selected from group 14 of the periodic table. Alternatively, a quaternary group III-IV containing two types of elements (first element) selected from group 13 of the periodic table and two types of elements (second element) selected from group 14 of the periodic table It may be a group compound semiconductor.
The group III-IV compound semiconductor may contain an element other than group 13 and group 14 of the periodic table as a doping element.

(Group III-VI compound semiconductor crystal fine particles)
The Group III-VI compound semiconductor includes an element selected from Group 13 of the periodic table and an element selected from Group 16.
A binary group III-VI compound semiconductor containing an element selected from group 13 of the periodic table (first element) and an element selected from group 16 of the periodic table (second element) is, 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 include It is done.
A group III-VI compound semiconductor containing an element selected from group 13 of the periodic table (first element) and an element selected from group 16 of the periodic table (second element) is selected from group 13 of the periodic table. It may be a ternary group III-VI compound semiconductor containing one kind of element (first element) and two kinds of elements (second element) selected from group 16 of the periodic table, or a periodic table A ternary Group III-VI compound semiconductor comprising two types of elements selected from Group 13 (first element) and one type of element selected from Group 16 of the periodic table (second element). Alternatively, a quaternary group III-VI containing two types of elements (first element) selected from group 13 of the periodic table and two types of elements (second element) selected from group 16 of the periodic table It may be a group compound semiconductor.
The Group III-VI compound semiconductor may contain an element other than Groups 13 and 16 of the periodic table as a doping element.

(Group IV-VI compound semiconductor crystal fine particles)
The group IV-VI compound semiconductor includes an element selected from group 14 of the periodic table and an element selected from group 16. Examples of binary group IV-VI group compound semiconductors containing an element selected from group 14 of the periodic table (first element) and an element selected from group 16 of the periodic table (second element) include PbS , PbSe, PbTe, SnS, SnSe, or SnTe.
A Group IV-VI compound semiconductor including an element selected from Group 14 of the periodic table (first element) and an element selected from Group 16 of the periodic table (second element) is selected from Group 14 of the periodic table. It may be a ternary group IV-VI compound semiconductor containing one type of element (first element) and two types of elements (second element) selected from group 16 of the periodic table, or a periodic table A ternary group IV-VI compound semiconductor comprising two types of elements (first element) selected from group 14 and one type of element (second element) selected from group 16 of the periodic table. Alternatively, a quaternary group IV-VI containing two types of elements (first elements) selected from group 14 of the periodic table and two types of elements (second elements) selected from group 16 of the periodic table It may be a group compound semiconductor.
The group IV-VI compound semiconductor may contain an element other than group 14 and group 16 of the periodic table as a doping element.

(Transition metal-p-block compound semiconductor crystal fine particles)
The transition metal-p-block compound semiconductor includes an element selected from transition metal elements and an element selected from p-block elements.
As a binary transition metal-p-block compound semiconductor including an element selected from the transition metal element of the periodic table (first element) and an element selected from the p-block element of the periodic table (second element), For example, NiS and CrS are mentioned.
A transition metal-p-block compound semiconductor including an element selected from a transition metal element of the periodic table (first element) and an element selected from the p-block element of the periodic table (second element) is a transition of the periodic table. Even a ternary transition metal-p-block compound semiconductor including one kind of element (first element) selected from metal elements and two kinds of elements (second elements) selected from p-block elements Or a ternary transition metal comprising two types of elements (first elements) selected from transition metal elements of the periodic table and one type of element (second elements) selected from p-block elements of the periodic table It may be a p-block compound semiconductor, or two elements (first element) selected from transition metal elements in the periodic table and two elements (second elements) selected from p-block elements in the periodic table A quaternary transition metal-p-bro It may be a click compound semiconductor.
The transition metal-p-block compound semiconductor may contain a transition metal element in the periodic table and an element other than the p-block element as a doping element.

Further, the ternary (ternary phase) semiconductor fine particles are a composition containing three elements selected from the group as described above, and can be represented by, for example, ZnCdS. The quaternary (quaternary phase) semiconductor fine particles are a composition containing four elements selected from the group as described above, and can be represented by, for example, ZnCdSSe.
These ternary and quaternary systems include CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgSe, CdHgSe, CdHgSe, CdHgSe, CdHgSe CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTTe, HgZnSeS, HgZnSeTe, HgZnSTe, GaNP, GaNAs, GaPAs, AlNP, AlNAs, AlPAs, InNP, InNAs, InPAs, InPAs CuInS _2, or InA PAs, and the like.

(Perovskite compound)
One example of the semiconductor fine particles of the present invention is fine particles of a perovskite compound.
The perovskite compound is a compound having a perovskite type crystal structure having A, B, and X as constituent components.
In the present invention, A is a component located at each vertex of a hexahedron centering on B in the perovskite crystal structure, and is a monovalent cation.
X represents a component located at each vertex of an octahedron centered on B in the perovskite crystal structure, and is one or more anions selected from the group consisting of halide ions and thiocyanate ions.
B is a component located at the center of the hexahedron that arranges A at the apex and the octahedron that arranges X at the apex in the perovskite crystal structure, and is a metal ion.

The perovskite compound having 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.
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 from −0.7 to 0.7.
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 compound is neutral (charge is 0). .
The three-dimensional structure has a three-dimensional network of vertex-sharing octahedrons represented by BX ₆ with B as the center and vertex as X.
In the case of the above two-dimensional structure, the octahedral pair represented by BX ₆ having B as the center and the vertex as X shares the four vertices X on the same plane, thereby BX ₆ connected two-dimensionally. The structure which the layer which consists of, and the layer which consists of A were laminated | stacked alternately is formed.
B is a metal cation capable of taking X octahedral coordination.
A is located at each vertex of a hexahedron centered on B.
In the present specification, the perovskite crystal structure can be confirmed by an X-ray diffraction pattern.
In the case of a compound having a three-dimensional perovskite crystal structure, the peak derived from (hkl) = (001) or 2θ = 18 to 25 at the position of 2θ = 12 to 18 °, usually in the X-ray diffraction pattern. A peak derived from (hkl) = (100) is confirmed at the position of °. A peak derived from (hkl) = (001) is observed at the position of 2θ = 13 to 16 °, or a peak derived from (hkl) = (100) is confirmed at the position of 2θ = 20 to 23 °. Is more preferable.
In the case of the compound having the two-dimensional perovskite crystal structure, a peak derived from (hkl) = (002) is usually observed at a position of 2θ = 1 to 10 ° in the X-ray diffraction pattern. 2θ = 2 More preferably, a peak derived from (hkl) = (002) is confirmed at a position of ˜8 °.

The perovskite compound is preferably a perovskite compound represented by the following general formula (1).
ABX _{(3 + δ)} (−0.7 ≦ δ ≦ 0.7) (1)
[In General Formula (1), A is a monovalent cation, B is a metal ion, X is one or more anions selected from the group consisting of halide ions and thiocyanate ions. ]

[A]
In the perovskite compound according to the present invention, A is a component located at each vertex of a hexahedron centered on B in the perovskite crystal structure, and is a monovalent cation. Examples of the monovalent cation include cesium ion, organic ammonium ion, or amidinium ion. 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 is generally represented by ABX _{(3 + δ).} It has a three-dimensional structure.
In the compound, A is preferably a cesium ion or an organic ammonium ion.

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

In general formula (A3), R ⁶ to R ⁹ are each independently a hydrogen atom, an alkyl group which may have an amino group as a substituent, or a cyclo which may have an amino group as a substituent. Represents an alkyl group. However, not all of R ⁶ to R ⁹ are hydrogen atoms.

The alkyl group represented by R ⁶ to R ⁹ may be linear or branched, and may have an amino group as a substituent.
The number of carbon atoms of the alkyl group represented by R ⁶ to R ⁹ is usually 1 to 20, preferably 1 to 4, and more preferably 1 to 3.

The cycloalkyl group represented by R ⁶ to R ⁹ may have an alkyl group or an amino group as a substituent.
The number of carbon atoms of the cycloalkyl group represented by R ⁶ to R ⁹ is 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.

The groups represented by R ⁶ to R ⁹ are each independently preferably a hydrogen atom or an alkyl group.
A perovskite crystal having a three-dimensional structure with high emission intensity by reducing the number of alkyl groups and cycloalkyl groups that can be included in the general formula (A3), and by reducing the number of carbon atoms of the alkyl group and cycloalkyl group. A compound having a structure can be obtained.
When the alkyl group or cycloalkyl group has 4 or more carbon atoms, a compound having a two-dimensional and / or pseudo two-dimensional (quasi-2D) perovskite crystal structure in part or in whole can be obtained. When the two-dimensional perovskite crystal structure is stacked infinitely, it becomes equivalent to the three-dimensional perovskite crystal structure (reference: PP Boix et al., J. Phys. Chem. Lett. 2015, 6, 898-907. Such).
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, and one of R ⁶ to R ⁹ is 1 to 3 carbon atoms. More preferably, three of R ⁶ to R ⁹ are hydrogen atoms.

Examples of the alkyl group of R ⁶ to R ⁹ include 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, and an isopentyl group. , Neopentyl, tert-pentyl, 1-methylbutyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, n-heptyl 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 R 6 ^~ exemplified alkyl group having 3 or more carbon atoms in the alkyl group R ⁹ is to form a ring, as an example, a cyclopropyl group, a cyclobutyl group And cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, norbornyl group, isobornyl group, 1-adamantyl group, 2-adamantyl group, tricyclodecyl group and the like.

As the organic ammonium ion represented by A, CH ₃ NH ₃ ⁺ (also referred to as methylammonium ion), C ₂ H ₅ NH ₃ ⁺ (also referred to as 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 still more preferably CH ₃ NH ₃ ⁺ .

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

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

The alkyl group represented by R ¹⁰ to R ¹³ may be linear or branched, and may have an amino group as a substituent.
The number of carbon atoms in the alkyl group represented by R ¹⁰ ~ ^{R 13} is generally 1 to 20, preferably 1 to 4, and more preferably 1-3.

The cycloalkyl group represented by R ¹⁰ to R ¹³ may have an alkyl group or an amino group as a substituent.
The number of carbon atoms of the cycloalkyl group represented by R ¹⁰ to R ¹³ is usually 3 to 30, preferably 3 to 11, and more preferably 3 to 8. The number of carbon atoms includes the number of carbon atoms of the substituent.

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

The group represented by R ¹⁰ to R ¹³ is preferably a hydrogen atom or an alkyl group.
By reducing the number of alkyl groups and cycloalkyl groups included in the general formula (A4), and by reducing the number of carbon atoms in the alkyl groups and cycloalkyl groups, a perovskite compound having a three-dimensional structure with high emission intensity is obtained. Obtainable.
When the number of carbon atoms in the alkyl group or cycloalkyl group is 4 or more, a compound having a two-dimensional and / or pseudo two-dimensional (quasi-2D) perovskite crystal structure in part or in whole can be obtained. 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. R ¹¹ to R ¹³ are more preferably hydrogen atoms.

[B]
In the perovskite compound, B is a component located in the center of a hexahedron in which A is arranged at the apex and an octahedron in which X is arranged at the apex in the perovskite crystal structure, and represents a metal ion. The B component metal ion may be an ion composed of one or more selected from the group consisting of a monovalent metal ion, a divalent metal ion, and a trivalent metal ion. B preferably contains a divalent metal ion, and more preferably contains one or more metal ions selected from the group consisting of lead and tin.

[X]
X represents one or more anions selected from the group consisting of halide ions and thiocyanate ions. X may be one or more anions selected from the group consisting of chloride ions, bromide ions, fluoride ions, iodide ions, and thiocyanate ions.
X can be appropriately selected according to the desired emission wavelength. For example, X can contain bromide ions.
When X is two or more types of halide ions, the content ratio of the halide ions can be appropriately selected according to the emission wavelength, for example, a combination of bromide ions and chloride ions, or bromide ions and iodides. It can be a combination with ions.

Specific examples of the perovskite compound having a three-dimensional perovskite crystal structure represented by ABX _{(3 + δ)} include CH ₃ NH ₃ PbBr ₃ , CH ₃ NH ₃ PbCl ₃ , and CH ₃ NH. ₃ PbI ₃ , CH ₃ NH ₃ PbBr _(3-y) I _y (0 <y <3), CH ₃ NH ₃ PbBr _(3-y) Cl _y (0 <y <3), (H ₂ N═CH —NH ₂ ) PbBr ₃ , (H ₂ N═CH—NH ₂ ) PbCl ₃ , (H ₂ N═CH—NH ₂ ) PbI ₃ , CH ₃ NH ₃ Pb _(1-a) Ca _a Br _{(3 + δ)} ( 0 <a ≦ 0.7, 0 ≦ δ ≦ 0.7), CH ₃ NH ₃ Pb _(1-a) Sr _a Br _{(3 + δ)} (0 <a ≦ 0.7, 0 ≦ δ ≦ 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 + δ) (0 <a ≦ 0.7,0 ≦ δ ≦ 0.7) CH ₃ NH ₃ Pb _(1-a) Dy _a Br _{(3 + δ)} (0 <a ≦ 0.7, 0 ≦ δ ≦ 0.7), CH ₃ NH ₃ Pb _(1-a) Na _a Br _{(3 + δ ) (0 <a ≦ 0.7,} -0.7 ≦ δ ≦ 0), CH 3 NH 3 Pb (1-a) Li a Br (3 + δ) (0 <a ≦ 0.7, -0.7 ≦ δ ≦ 0), CsPb _(1-a) Na _a Br _{(3 + δ)} (0 <a ≦ 0.7, −0.7 ≦ δ ≦ 0), CsPb _(1-a) Li _a Br _{(3 + δ)} (0 <A ≦ 0.7, −0.7 ≦ δ ≦ 0), CH ₃ NH ₃ Pb _(1-a) Na _a Br _{(3 + δ−y)} I _y (0 <a ≦ 0.7, −0.7 ≦ δ ≦ 0, 0 <y <3), CH ₃ NH ₃ Pb _(1-a) Li _a Br _{(3 + δ−y)} I _y (0 <a ≦ 0.7, −0.7 ≦ δ ≦ 0, 0 <y <3), CH ₃ NH ₃ Pb _{(1- a)} Na _a Br _{(3 + δ−y)} Cl _y (0 <a ≦ 0.7, −0.7 ≦ δ ≦ 0, 0 <y <3), CH ₃ NH ₃ Pb _(1-a) Li _a Br _{(3 + δ−y)} Cl _y (0 <a ≦ 0.7, −0.7 ≦ δ ≦ 0, 0 <y <3), (H ₂ N═CH—NH ₂ ) Pb _(1-a) Na _a Br _{(3 + δ)} (0 <a ≦ 0.7, −0.7 ≦ δ ≦ 0), (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 _{_{) Pb (1-a) Na}} a Br (3 + δ-y) Cl y (0 <a ≦ 0.7, -0.7 ≦ δ ≦ 0, 0 <y <3), CsPbBr 3, CsPbCl 3, CsPbI 3 , CsPbBr _(3-y) I _y (0 <y <3), CsPbBr _(3-y) Cl _y (0 <y <3), CH ₃ NH ₃ PbBr _(3-y) Cl _y (0 <y < 3), CH ₃ NH ₃ Pb _(1-a) Zn _a Br _{(3 + δ)} (0 <a ≦ 0.7, 0 ≦ δ ≦ 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 + δ)} (0 <a ≦ 0.7, 0 ≦ δ ≦ 0.7), CH ₃ NH ₃ Pb _(1-a) Mn _a Br _{(3 + δ)} (0 <a ≦ 0.7, 0 ≦ δ ≦ 0.7), CH ₃ NH ₃ Pb _(1-a) Mg _a Br _{(3 + δ)} (0 <a ≦ 0.7, 0 ≦ δ ≦ 0.7), CsPb _(1-a) Zn _a Br _{(3 + δ)} (0 <a ≦ 0.7, 0 ≦ δ ≦ 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 + δ) )} (0 <a ≦ 0.7, 0 ≦ δ ≦ 0.7), CsPb _(1-a) Mn _a Br _{(3 + δ)} (0 <a ≦ 0.7, 0 ≦ δ ≦ 0.7), CsPb _(1-a) Mg _a Br _{(3 + δ)} (0 <a ≦ 0.7, 0 ≦ δ ≦ 0.7), CH ₃ NH ₃ Pb _(1-a) Zn _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) 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 + δ-y) I y (0 <a ≦ 0.7,0 ≦ δ ≦ 0.7,0 <y <3), CH 3 NH 3 Pb _(1-a) Mn _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) Mg _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) Zn _a Br _{(3 + δ−y) )} Cl _y (0 <a ≦ 0.7, 0 ≦ δ ≦ 0.7, 0 <y <3), CH ₃ NH ₃ Pb _(1-a) Al _a Br _{(3 + δ−y)} Cl _y (0 < a ≦ 0.7, 0 ≦ _δ ≦ 0.7, 0 <y <3), CH ₃ NH ₃ Pb _(1-a) Co _a Br _{(3 + δ−y)} Cl _y (0 <a ≦ 0.7, 0 ≦ δ ≦ 0.7,0 <y < 3), CH _{_{_{NH 3 Pb (1-a)}}} Mn a Br (3 + δ-y) Cl y (0 <a ≦ 0.7,0 ≦ δ ≦ 0.7,0 <y <3), CH 3 NH 3 Pb (1- _a) Mg _a Br _{(3 + δ−y)} Cl _y (0 <a ≦ 0.7, 0 ≦ δ ≦ 0.7, 0 <y <3), (H ₂ N═CH—NH ₂ ) Zn _a Br _{( 3 + δ)} (0 <a ≦ 0.7, 0 ≦ δ ≦ 0.7), (H ₂ N═CH—NH ₂ ) Mg _a Br _{(3 + δ)} (0 <a ≦ 0.7, 0 ≦ δ ≦ 0) .7), (H ₂ N═CH—NH ₂ ) Pb _(1-a) Zn _a Br _{(3 + δ−y)} I _y (0 <a ≦ 0.7, 0 ≦ δ ≦ 0.7, 0 <y <3), (H ₂ N═CH—NH ₂ ) Pb _(1-a) Zn _a Br _{(3 + δ−y)} Cl _y (0 <a ≦ 0.7, 0 ≦ δ ≦ 0.7, 0 <y <3) etc. are mentioned as a preferable thing.

Specific examples of the perovskite compound having a two-dimensional perovskite crystal structure represented by A ₂ BX _{(4 + δ)} include (C ₄ H ₉ NH ₃ ) ₂ PbBr ₄ , (C ₄ H ₉ NH ₃ ) ₂ PbCl ₄ , (C ₄ H ₉ NH ₃ ) ₂ PbI ₄ , (C ₇ H ₁₅ NH ₃ ) ₂ PbBr ₄ , (C ₇ H ₁₅ NH ₃ ) ₂ PbCl ₄ , (C ₇ H ₁₅ NH ₃ ) ₂ PbI ₄ , (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Li _a Br ₄ (0 <a ≦ 0.7), (C ₄ H ₉ NH ₃ ) ₂ Pb _{(1-a )} Na _a Br ₄ (0 <a ≦ 0.7), (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Rb _a Br ₄ (0 <a ≦ 0.7), (C ₇ H ₁₅ NH ₃ ) ₂ Pb _(1-a) Na _a Br ₄ (0 <a ≦ 0.7), (C ₇ H ₁₅ NH ₃ ) ₂ Pb _(1-a) Li _a Br ₄ (0 <a ≦ 0.7), (C ₇ H ₁₅ NH ₃ ) ₂ Pb _(1-a) Rb _a Br ₄ (0 <a ≦ 0.7), ( C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Na _a Br _(4-y) I _y (0 <a ≦ 0.7, 0 <y <4), (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Li _a Br _(4-y) I _y (0 <a ≦ 0.7, 0 <y <4), (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Rb _a Br _{( 4-y)} I _y (0 <a ≦ 0.7, 0 <y <4), (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Na _a Br _(4-y) Cl _y (0 < a ≦ 0.7, 0 <y <4), (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Li _a Br _(4-y) Cl _y (0 <a ≦ 0.7, 0 <y <4), (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Rb _a B r _(4-y) Cl _y (0 <a ≦ 0.7, 0 <y <4), (C ₄ H ₉ NH ₃ ) ₂ PbBr ₄ , (C ₇ H ₁₅ NH ₃ ) ₂ PbBr ₄ , (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), (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Zn _a Br _{(4 + δ)} (0 <a ≦ 0.7), (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Mg _a Br _{(4 + δ)} (0 <a ≦ 0.7, 0 ≦ δ ≦ 0.7) (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Co _a Br _{(4 + δ)} (0 <a ≦ 0.7, 0 ≦ δ _{_{≦ 0.7), (C 4 H}} 9 NH 3) 2 Pb (1-a) Mn a Br (4 + δ) (0 <a ≦ 0.7,0 ≦ δ ≦ 0.7), (C 7 H 15 _{_{_{NH 3) 2 Pb (1-}}} a) Zn a B _{(4 + δ) (0 <} a ≦ 0.7,0 ≦ δ ≦ 0.7), (C 7 H 15 NH 3) 2 Pb (1-a) Mg a Br (4 + δ) (0 <a ≦ 0.7 , 0 ≦ δ ≦ 0.7), (C ₇ H ₁₅ NH ₃ ) ₂ Pb _(1-a) Co _a Br _{(4 + δ)} (0 <a ≦ 0.7, 0 ≦ δ ≦ 0.7), ( C ₇ H ₁₅ NH ₃ ) ₂ Pb _(1-a) Mn _a Br _{(4 + δ)} (0 <a ≦ 0.7, 0 ≦ δ ≦ 0.7), (C ₄ H ₉ NH ₃ ) ₂ Pb _{(1 -A)} Zn _a Br _{(4 + δ-y)} I _y (0 <a ≦ 0.7, 0 ≦ δ ≦ 0.7, 0 <y <4), (C ₄ H ₉ NH ₃ ) ₂ Pb _{(1- a)} Mg _a Br _{(4 + δ−y)} I _y (0 <a ≦ 0.7, 0 ≦ δ ≦ 0.7, 0 <y <4), (C ₄ H ₉ NH ₃ ) ₂ Pb _{(1-a )} Co _a Br _{(4 + δ−y)} I _y (0 <a ≦ 0.7, 0 ≦ δ ≦ 0) .7, 0 <y <4), (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Mn _a Br _{(4 + δ-y)} I _y (0 <a ≦ 0.7, 0 ≦ δ ≦ 0. 7, 0 <y <4), (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Zn _a Br _{(4 + δ−y)} Cl _y (0 <a ≦ 0.7, 0 ≦ δ ≦ 0.7 , 0 <y <4), (C 4 H 9 NH 3) 2 Pb (1-a) Mg a Br (4 + δ-y) Cl y (0 <a ≦ 0.7,0 ≦ δ ≦ 0.7, 0 ≦ δ ≦ 0.7, 0 <y <4), (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Co _a Br _{(4 + δ−y)} Cl _y (0 <a ≦ 0.7, 0 ≦ δ ≦ 0.7, 0 <y <4), (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Mn _a Br _{(4 + δ-y)} Cl _y (0 <a ≦ 0.7, 0 ≦ δ ≦ 0.7, 0 <y <4) and the like are preferable.

≪Emission spectrum≫
The perovskite compound is an illuminant capable of emitting fluorescence in the visible light wavelength region. When X is a bromide ion, it is usually 480 nm or more, preferably 500 nm or more, more preferably 520 nm or more, and usually 700 nm or less, preferably Can emit fluorescence having a maximum intensity peak in a wavelength range of 600 nm or less, more preferably 580 nm or less.
The above upper limit value and lower limit value can be arbitrarily combined.
As another aspect of the present invention, when X in the perovskite compound is a bromide ion, the fluorescence peak emitted is usually 480 to 700 nm, preferably 500 to 600 nm, more preferably 520 to 580 nm. preferable.
When X is an iodide ion, it is usually a peak of intensity in a wavelength range of 520 nm or more, preferably 530 nm or more, more preferably 540 nm or more, and usually 800 nm or less, preferably 750 nm or less, more preferably 730 nm or less. There can be some fluorescence.
The above upper limit value and lower limit value can be arbitrarily combined.
As another aspect of the present invention, 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 preferably 540 to 730 nm. More preferred.
When X is a chloride ion, it is usually at least 300 nm, preferably 310 nm or more, more preferably 330 nm or more, and usually 600 nm or less, preferably 580 nm or less, more preferably 550 nm or less in the range of the maximum intensity peak. There can be some fluorescence.
The above upper limit value and lower limit value can be arbitrarily combined.
As another aspect of the present invention, when X in the perovskite compound is a chloride ion, the fluorescence peak emitted is usually 300 to 600 nm, preferably 310 to 580 nm, and preferably 330 to 550 nm. More preferred.

(2) Organic compound having amino group, alkoxy group and silicon atom The organic compound having amino group, alkoxy group and silicon atom may be an organic compound having amino group and alkoxysilyl group.
The organic compound having an amino group, an alkoxy group, and a silicon atom may be an organic compound having an amino group, an alkoxy group, and a silicon atom represented by the following general formula (A5).
The organic compound represented by the following general formula (A5) has an amino group and an alkoxysilyl group.

In general formula (A5), A is a divalent hydrocarbon group, O is an oxygen atom, N is a nitrogen atom, Si is a silicon atom, and R ¹⁴ to R ¹⁵ are each independently a hydrogen atom, an alkyl group, Or a cycloalkyl group, R ¹⁶ represents an alkyl group or a cycloalkyl group, and R ^{17 to} R ¹⁸ represent a hydrogen atom, an alkyl group, an alkoxy group, or a cycloalkyl group.

When R ¹⁴ to R ¹⁸ are alkyl groups, they may be linear or branched.
The alkyl group usually has 1 to 20 carbon atoms, preferably 5 to 20, and more preferably 8 to 20.

When R ¹⁴ to R ¹⁸ are cycloalkyl groups, the cycloalkyl group may have an alkyl group as a substituent. The number of carbon atoms in the cycloalkyl group is usually 3 to 30, preferably 3 to 20, and more preferably 3 to 11. The number of carbon atoms includes the number of carbon atoms of the substituent.

Specific examples of the alkyl group for R ¹⁴ to R ¹⁸ include the alkyl groups exemplified for R ⁶ to R ⁹ .
Specific examples of the cycloalkyl group represented by R ¹⁴ to R ¹⁸ include the cycloalkyl groups exemplified for R ⁶ to R ⁹ .
Examples of the alkoxy group of R ¹⁷ to R ¹⁸ include monovalent groups in which the linear or branched alkyl group exemplified for R ⁶ to R ⁹ is bonded to an oxygen atom.

When R ¹⁷ to R ¹⁸ are alkoxy groups, examples thereof include a methoxy group, an ethoxy group, and a butoxy group, and a methoxy group is preferable.

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

A part or all of the organic compound having an amino group, an alkoxy group, and an organic compound having a silicon atom represented by the general formula (A5) may be adsorbed on the surface of the semiconductor fine particles according to the present invention. It may be dispersed in the object.
Examples of the organic compound having an amino group, an alkoxy group, and a silicon atom represented by the general formula (A5) include trimethoxy [3- (methylamino) propyl] silane, 3-aminopropyltriethoxysilane, and 3-aminopropyldimethoxy. Methylsilane, 3-aminopropyldiethoxymethylsilane, and 3-aminopropyltrimethoxysilane are preferable, and 3-aminopropyltrimethoxysilane is more preferable.

As the organic compound of (2), in the organic compound represented by the general formula (A5), R ¹⁴ and R ¹⁵ are hydrogen atoms, R ¹⁶ is the alkyl group, and R ¹⁷ and R ¹⁸ are alkoxy. Compounds that are groups are preferred.
Another aspect of the present invention is (2) an organic compound having an amino group, an alkoxy group, and a silicon atom, and an ionicity other than a group represented by —NH ₃ ⁺ and a group represented by —COO 2 ^— . Organic compounds having a group and compounds having a mercapto group can be excluded.

(3) At least one selected from the group consisting of a polymerizable compound and a polymer The polymerizable compound contained in the composition according to the present invention is not particularly limited, but at the temperature at which the composition is produced. Those having low solubility in the polymerizable compound of the semiconductor fine particles are preferable.
In the present specification, the “polymerizable compound” means a monomer compound having a polymerizable group.
For example, when producing at room temperature and normal pressure, the polymerizable compound is not particularly limited, and examples thereof include known polymerizable compounds such as styrene and methyl methacrylate. Especially, as a polymeric compound, any one or both of acrylic acid ester and methacrylic acid ester which are the monomer components of acrylic resin are preferable.

The polymer contained in the composition according to the present invention is not particularly limited, but a polymer having low solubility of the semiconductor fine particles in the polymer at the temperature for producing the composition is preferable.
For example, in the case of producing at room temperature and normal pressure, the polymer is not particularly limited, and examples thereof include known polymers such as polystyrene and methacrylic resin. Especially, as a polymer, acrylic resin is preferable. The acrylic resin includes a structural unit derived from an acrylate ester and / or a methacrylate ester.
Among the structural units of the polymerizable compound (3) and the polymer, acrylic acid ester and / or methacrylic acid ester and structural units derived therefrom are 10% with respect to all structural units when expressed in mol%. It may be above, 30% or more, 50% or more, 80% or more, or 100%.

(4) At least one selected from the group consisting of ammonia, amine, and carboxylic acid, and salts or ions thereof. The composition according to the present invention is in a form that ammonia, amine, carboxylic acid, and the compound can take. In addition, at least one selected from the group consisting of these salts or ions may be included.
That is, the composition according to the present invention is (2) a compound other than an organic compound having an amino group, an alkoxy group, and a silicon atom, and is ammonia, amine, carboxylic acid, ammonia salt, amine salt, carboxylic acid And at least one selected from the group consisting of salts of ammonia, ammonia ions, amine ions, and carboxylic acid ions.
Ammonia, amines and carboxylic acids and their salts or ions usually act as capping ligands. The capping ligand is a compound having an action of adsorbing on the surface of the semiconductor compound and stably dispersing the semiconductor compound in the composition. Examples of the ion or salt (ammonium salt or the like) of ammonia or amine include an ammonium cation represented by the general formula (A1) described later and an ammonium salt containing the ammonium cation. Examples of the carboxylic acid ion or salt (carboxylate and the like) include a carboxylate anion represented by the general formula (A2) described later and a carboxylate containing the carboxylate anion. The composition according to the present invention may contain any one of an ammonium salt and the like, a carboxylate and the like, or may contain both.

Examples of ammonium salts include ammonium salts containing an ammonium cation represented by the general formula (A1).

In general formula (A1), R ¹ to R ⁴ each independently represents a hydrogen atom or an organic group. When it is an organic group, R ¹ to R ⁴ are preferably each independently a hydrocarbon group such as an alkyl group, a cycloalkyl group, or an unsaturated hydrocarbon group.

The alkyl group represented by R ¹ to R ⁴ may be linear or branched.
The number of carbon atoms of the alkyl group represented by R ¹ to R ⁴ is usually 1 to 20, preferably 5 to 20, and more preferably 8 to 20.

The cycloalkyl group represented by R 1 ^~ R ⁴ may have an alkyl group as a substituent. The number of carbon atoms in the cycloalkyl group is usually 3 to 30, preferably 3 to 20, and more preferably 3 to 11. The number of carbon atoms includes the number of carbon atoms of the substituent.

The unsaturated hydrocarbon group for R ¹ to R ⁴ may be linear or branched.
The number of carbon atoms of the unsaturated hydrocarbon group of R ¹ to R ⁴ is usually 2 to 20, preferably 5 to 20, and more preferably 8 to 20.

R ¹ to R ⁴ are preferably a hydrogen atom, an alkyl group, or an unsaturated hydrocarbon group. As the unsaturated hydrocarbon group, an alkenyl group is preferable. More preferably, ^{one of} R ¹ to R ⁴ is an alkenyl group having 8 to 20 carbon atoms, and three of R ¹ to R ⁴ are hydrogen atoms.

Specific examples of the alkyl group for R ¹ to R ⁴ include the alkyl groups exemplified for R ⁶ to R ⁹ .
As specific examples of the cycloalkyl group of R ¹ ~ ^{R 4} ^include cycloalkyl groups exemplified in ^R 6 ~ R ^9.

As the alkenyl group for R ¹ to R ⁴ , a single bond (C—C) between any one carbon atom in the linear or branched alkyl group exemplified for R ⁶ to R ⁹ is 2 The thing substituted by the heavy bond (C = C) can be illustrated, and the position of a double bond is not limited.
Preferred examples of such an alkenyl group 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.

The counter anion is not particularly limited, but preferable examples include Br ⁻ , Cl ⁻ , I ⁻ and F ⁻ halide ions, and carboxylate ions.
Preferred examples of the ammonium salt having an ammonium cation represented by the general formula (A1) and a counter anion include n-octyl ammonium salt and oleyl ammonium salt.

As carboxylate, the carboxylate containing the carboxylate anion represented with the following general formula (A2) is mentioned.
R ⁵ —CO ₂ ^— (A2)

In general formula (A2), R ⁵ represents a monovalent organic group. As the organic group, a hydrocarbon group is preferable, and among them, an alkyl group, a cycloalkyl group, and an unsaturated hydrocarbon group are preferable.

The alkyl group represented by R ⁵ may be linear or branched. The number of carbon atoms of the alkyl group represented by R ⁵ is usually 1 to 20, preferably 5 to 20, and more preferably 8 to 20.

The cycloalkyl group represented by R ⁵ may have an alkyl group as a substituent. The number of carbon atoms in the cycloalkyl group is usually 3 to 30, preferably 3 to 20, and more preferably 3 to 11. The number of carbon atoms includes the number of carbon atoms of the substituent.

The unsaturated hydrocarbon group for R ⁵ may be linear or branched.
The number of carbon atoms of the unsaturated hydrocarbon group for R ⁵ is usually 2 to 20, preferably 5 to 20, and more preferably 8 to 20.

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

Specific examples of the alkyl group R ⁵ include alkyl groups exemplified in R 6 ^~ R ^9.
Specific examples of the cycloalkyl group represented by R ⁵ include the cycloalkyl groups exemplified for R ⁶ to R ⁹ .
Specific examples of the alkenyl group for R ⁵ include the alkenyl groups exemplified for R ¹ to R ⁴ .

The carboxylate anion represented by the general formula (A2) is preferably an oleate anion. The counter cation of the carboxylate anion represented by the general formula (A2) is not particularly limited, but preferred examples include proton, alkali metal cation, alkaline earth metal cation, ammonium cation and the like.

(Others) Solvent The solvent that may be contained in the composition according to the present invention includes a medium in which the semiconductor fine particles can be dispersed and the semiconductor fine particles are difficult to dissolve.
In this specification, the “solvent” refers to a substance that takes a liquid state at 1 atm and 25 ° C. (except for a polymerizable compound and a polymer).

Examples of the solvent include esters such as methyl formate, ethyl formate, propyl formate, pentyl formate, methyl acetate, ethyl acetate, and pentyl acetate; γ-butyrolactone, acetone, dimethyl ketone, diisobutyl ketone, cyclopentanone, Ketones such as cyclohexanone and methylcyclohexanone; diethyl ether, methyl-tert-butyl ether, diisopropyl ether, dimethoxymethane, dimethoxyethane, 1,4-dioxane, 1,3-dioxolane, 4-methyldioxolane, tetrahydrofuran, methyltetrahydrofuran, anisole, Ethers such as phenetole; 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 Alcohols such as -1-propanol; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, triethylene glycol dimethyl ether; N-methyl-2-pyrrolidone, N, Organic solvents having an amide group such as N-dimethylformamide, acetamide, N, N-dimethylacetamide; acetonitrile, isobutyronitrile, propionitrile, methoxyacetate Organic solvents having a nitrile group such as tonitrile; organic solvents having a hydrocarbon group such as ethylene carbonate and propylene carbonate; organic solvents having a halogenated hydrocarbon group such as methylene chloride and chloroform; n-pentane, cyclohexane, n- Organic solvents having a hydrocarbon group such as hexane, benzene, toluene, xylene; dimethyl sulfoxide and the like.

Among these, esters such as methyl formate, ethyl formate, propyl formate, pentyl formate, methyl acetate, ethyl acetate, pentyl acetate; γ-butyrolactone, acetone, dimethyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methyl Ketones such as cyclohexanone; diethyl ether, methyl-tert-butyl ether, diisopropyl ether, dimethoxymethane, dimethoxyethane, 1,4-dioxane, 1,3-dioxolane, 4-methyldioxolane, tetrahydrofuran, methyltetrahydrofuran, anisole, phenetole, etc. Organic solvents having a nitrile group such as ether, acetonitrile, isobutyronitrile, propionitrile, methoxyacetonitrile; Organic solvents having carbonate groups such as tylene carbonate and propylene carbonate; organic solvents having halogenated hydrocarbon groups such as methylene chloride and chloroform; hydrocarbons such as n-pentane, cyclohexane, n-hexane, benzene, toluene and xylene An organic solvent having a group is preferable because it has low polarity and hardly dissolves semiconductor fine particles, and is preferably an organic solvent having a halogenated hydrocarbon group such as methylene chloride or chloroform; n-pentane, cyclohexane, n-hexane, More preferred are hydrocarbon-based organic solvents such as benzene, toluene and xylene.

<About the mixing ratio of each component>
The composition of this embodiment contains (1), (2), and (3).
(1) Semiconductor fine particles (2) Organic compounds having amino groups, alkoxy groups, and silicon atoms (3) At least one selected from the group consisting of polymerizable compounds and polymers

The composition of the present embodiment is a composition that includes (1), (2), and (3 ′), and the total of (1), (2), and (3 ′) is 90% by mass or more. May be.
(1) Semiconductor fine particles (2) Organic compound having amino group, alkoxy group, and silicon atom (3 ′) polymer

In the composition of this embodiment, the blending ratio of (1) and (2) may be such that the effect of improving the thermal durability by the organic compound of (2) is exhibited. It can be appropriately determined according to the type of 2).
In the composition of the present embodiment, (1) when the semiconductor fine particles are fine particles of a perovskite compound, the molar ratio [(2) / B] of the B metal ion of the perovskite compound and the organic compound of (2) is: It may be 0.001 to 1000, 0.01 to 700, or 0.1 to 500.
In the composition of this embodiment, (1) the semiconductor fine particles are fine particles of a perovskite compound, and the organic compound (2) has an amino group, an alkoxy group, and a silicon atom represented by the general formula (A5) In the case of a compound, the molar ratio [(A5) / B] between the metal ion of B of the perovskite compound and the organic compound of (A5) may be 1 to 500, or 2 to 300 It may be 5 to 200 or 10 to 100.
A composition in which the range of the blending ratio of (1) and (2) is within the above range is preferable in that the effect of improving the heat durability by the organic compound of (2) is exhibited particularly well.
As another aspect of the present invention, (1) the semiconductor fine particles are fine particles of a perovskite compound, and the organic compound (2) contains an amino group, an alkoxy group, and a silicon atom represented by the general formula (A5). The molar ratio [(A5) / B] of the B metal ion of the perovskite compound to the organic compound (A5) is preferably 1 to 200, and more preferably 5 to 100. More preferably, it is more preferably 20 to 80, and particularly preferably 30 to 60.

In the composition of the present embodiment including (1), (2), and (3), the compounding ratio between (1) and (3) is such that the light emitting action by the semiconductor fine particles of (1) is satisfactorily exhibited. It can be determined as appropriate according to the types (1) to (3).
In the composition of the present embodiment, the mass ratio [(1) / (3)] between (1) and (3) may be 0.00001 to 10, or 0.0001 to 1. Or 0.0005 to 0.1.
The composition in which the range related to the blending ratio of (1) and (3) is within the above range is preferable in that the aggregation of the semiconductor fine particles of (1) hardly occurs and the light emitting property is also exhibited well.

In the composition of this embodiment containing (1), (2), and (3 ′), the compounding ratio of (1) and (3 ′) is such that the light emitting action by the semiconductor fine particles of (1) is good. It is sufficient if it is an extent to be exhibited, and can be appropriately determined according to the types (1) and (3 ′).
In the composition of the present embodiment, the mass ratio [(1) / (3 ′)] between (1) and (3 ′) may be 0.00001 to 10, or 0.0001 to 1. It may be 0.0005 to 0.1.
A composition in which the range related to the blending ratio of (1) and (3 ′) is within the above range is preferable in that the light emitting property is satisfactorily exhibited.

<Method for producing composition>
Embodiments of the method for producing a composition according to the present invention will be described below. According to the method for producing the composition of the present embodiment, the composition of the embodiment according to the present invention can be produced. In addition, the composition of this invention is not limited to what is manufactured by the manufacturing method of the composition of the following embodiment.

<(1) Manufacturing method of semiconductor fine particles>
(Group II-VI compound semiconductor crystal particles, Group II-V compound semiconductor crystal particles, Group III-V compound semiconductor crystal particles, Group III-IV compound semiconductor crystal particles, III Group-VI compound semiconductor crystal microparticles, Group IV-VI compound semiconductor crystal microparticles, and transition metal-p-block compound semiconductor crystal microparticle manufacturing method)
Examples of the method for producing semiconductor fine particles include a method of heating a mixed liquid obtained by mixing a simple substance of the elements constituting the semiconductor fine particles or a compound thereof and a lipophilic solvent.

Examples of the elemental element constituting the semiconductor fine particles or the compound thereof are not particularly limited, and examples thereof include metals, oxides, acetates, organometallic compounds, halides, and nitrates.

Examples of the fat-soluble solvent include nitrogen-containing compounds having a hydrocarbon group having 4 to 20 carbon atoms, oxygen-containing compounds having a hydrocarbon group having 4 to 20 carbon atoms, and the like. Examples of the hydrocarbon group having 4 to 20 carbon atoms include saturated aliphatic hydrocarbon groups such as n-butyl group, isobutyl group, n-pentyl group, octyl group, decyl group, dodecyl group, hexadecyl group and octadecyl group; An unsaturated aliphatic hydrocarbon group such as a group; an alicyclic hydrocarbon group such as a cyclopentyl group and a cyclohexyl group; an aromatic hydrocarbon group such as a phenyl group, a benzyl group, a naphthyl group, and a naphthylmethyl group. Of these, a saturated aliphatic hydrocarbon group and an unsaturated aliphatic hydrocarbon group are preferred. Examples of the nitrogen-containing compound include amines and amides, and examples of the oxygen-containing compound include fatty acids. Of these fat-soluble solvents, nitrogen-containing compounds having a hydrocarbon group having 4 to 20 carbon atoms are preferred. For example, n-butylamine, isobutylamine, n-pentylamine, n-hexylamine, octylamine, decylamine, Alkylamines such as dodecylamine, hexadecylamine and octadecylamine, and alkenylamines such as oleylamine are preferred. Such a fat-soluble solvent can be bonded to the particle surface, and examples of the bonding mode include chemical bonds such as a covalent bond, an ionic bond, a coordinate bond, a hydrogen bond, and a van der Waals bond.

The heating temperature of the mixed solution may be appropriately set depending on the simple substance or the compound to be used, but is preferably set in the range of 130 to 300 ° C, more preferably in the range of 240 to 300 ° C. . It is preferable that the heating temperature is equal to or higher than the lower limit because the crystal structure is easily unified. Further, the heating time may be appropriately set according to the simple substance to be used, the kind of the compound, and the heating temperature, but it is usually preferably set within the range of several seconds to several hours, and is set within the range of 1 to 60 minutes. Is more preferable.

In the method for producing semiconductor fine particles of the present invention, the heated mixed solution is cooled and then separated into a supernatant and a precipitate, and the separated semiconductor fine particles (precipitate) are separated from an organic solvent (for example, chloroform, toluene, hexane, n-butanol, etc.) Or a solution containing semiconductor fine particles. Alternatively, after cooling the mixed liquid after heating, it is separated into a supernatant and a precipitate, and a solvent (for example, methanol, ethanol, acetone, acetonitrile, etc.) in which nanoparticles are insoluble or hardly soluble is added to the separated supernatant and precipitated. The precipitate may be collected and placed in the above-mentioned organic solvent to form a solution containing semiconductor fine particles.

(Method for producing fine particles of perovskite compound crystals)
The semiconductor fine particles of the perovskite compound according to the present invention can be produced by the method described below with reference to known documents (Nano Lett. 2015, 15, 3692-3696, ACSNano, 2015, 9, 4533-4542).

<First Embodiment of Method for Producing Fine Crystalline Perovskite Compound>
For example, the method for producing semiconductor fine particles of the perovskite compound according to the present invention includes a step of dissolving a B component, an X component, and an A component in a solvent to obtain a solution, and the resulting solution and the solubility of the semiconductor fine particles in the solvent. And a step of mixing a solvent lower than the solvent used in the step of obtaining the solution.
More specifically, a step of dissolving a compound containing a B component and an X component and a component A or a compound containing an A component and an X component in a solvent to obtain a solution, the obtained solution, and a solvent for semiconductor fine particles And a step of mixing a solvent having a lower solubility than the solvent used in the step of obtaining the solution.
A step of adding a compound containing B component and X component and a component containing A component or A component and X component to a high temperature solvent to obtain a solution; and a step of cooling the obtained solution; The manufacturing method containing is mentioned.

Hereinafter, the step of dissolving the compound containing the B component and the X component and the component A or the compound containing the A component and the X component in a solvent to obtain a solution, the obtained solution, and the solubility of the semiconductor fine particles in the solvent are: A production method including a step of mixing a solvent lower than the solvent used in the step of obtaining a solution will be described.
In addition, solubility means the solubility in the temperature which performs the process to mix.
The manufacturing method preferably includes a step of adding a capping ligand from the viewpoint of stably dispersing the semiconductor fine particles. The capping ligand is preferably added before the mixing step, and the capping ligand may be added to a solution in which the A component, the B component, and the X component are dissolved. The solvent may be added to a solvent having a lower solubility than the solvent used in the step of obtaining the solution. The solution in which the A component, the B component, and the X component are dissolved, and the solubility of the semiconductor fine particles in the solvent You may add to both the solvent lower than the solvent used at the process to obtain.
The manufacturing method preferably includes a step of removing coarse particles by a method such as centrifugation or filtration after the mixing step. The size of the coarse particles removed by the removing step is preferably 10 μm or more, more preferably 1 μm or more, and further preferably 500 nm or more.

The step of mixing the solution and the solvent having a solubility of the semiconductor fine particles in the solvent lower than that of the solvent used in the step of obtaining the solution includes the step (I) of obtaining the solution by dissolving the solution of the semiconductor fine particles in the solvent. It may be a step of dripping in a solvent lower than the solvent used in step (II), and is a step of dripping, into the solution, a solvent whose solubility in the solvent of the semiconductor fine particles is lower than the solvent used in the step of obtaining the solution. However, from the viewpoint of improving dispersibility, (I) is preferable.
When dropping, it is preferable to stir from the viewpoint of improving dispersibility.
In the step of mixing the solution with a solvent in which the solubility of the semiconductor fine particles in the solvent is lower than the solvent used in the step of obtaining the solution, the temperature is not particularly limited, but the compound having a perovskite crystal structure is likely to precipitate. From the viewpoint of ensuring the thickness, it is preferably in the range of −20 to 40 ° C., more preferably in the range of −5 to 30 ° C.

The two types of solvents having different solubility in the solvent of the semiconductor fine particles used in the production method are not particularly limited. For example, 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 Alcohols such as tetrafluoro-1-propanol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, triethylene glycol dimethyl ether Glycol ethers such as ter; organic solvents having amide groups such as N, N-dimethylformamide, acetamide, N, N-dimethylacetamide; dimethyl sulfoxide, methyl formate, ethyl formate, propyl formate, pentyl formate, methyl Esters such as acetate, ethyl acetate, pentyl acetate; ketones such as γ-butyrolactone, N-methyl-2-pyrrolidone, acetone, dimethyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methylcyclohexanone; diethyl ether, methyl-tert- Butyl ether, diisopropyl ether, dimethoxymethane, dimethoxyethane, 1,4-dioxane, 1,3-dioxolane, 4-methyldioxolane, tetrahydrofuran, methyl ether Ethers such as trahydrofuran, anisole, phenetole; organic solvents having a nitrile group such as acetonitrile, isobutyronitrile, propionitrile, methoxyacetonitrile; organic solvents having a carbonate group such as ethylene carbonate, propylene carbonate; methylene chloride, An organic solvent having a halogenated hydrocarbon group such as chloroform; and two solvents selected from the group consisting of organic solvents having a hydrocarbon group such as n-pentane, cyclohexane, n-hexane, benzene, toluene, and xylene. It is done.

The solvent used in the step of obtaining the solution included in the production method is preferably a solvent having a high solubility in the solvent of the semiconductor fine particles. For example, when performing the step at room temperature (10 ° C. to 30 ° C.), 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, Alcohols such as 2,2-trifluoroethanol and 2,2,3,3-tetrafluoro-1-propanol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether Ether acetate, glycol ethers such as triethylene glycol dimethyl ether; and dimethyl sulfoxide; N, N- dimethylformamide, acetamide, N, organic solvents having an amide group such as N- dimethylacetamide.

The solvent used in the mixing step included in the production method is preferably a solvent having low solubility of the semiconductor fine particles in the solvent. For example, when performing the step at room temperature (10 ° C. to 30 ° C.), methyl formate, ethyl Formate, propyl formate, pentyl formate, esters such as methyl acetate, ethyl acetate, pentyl acetate; γ-butyrolactone, N-methyl-2-pyrrolidone, acetone, dimethyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methyl Ketones such as cyclohexanone; diethyl ether, methyl-tert-butyl ether, diisopropyl ether, dimethoxymethane, dimethoxyethane, 1,4-dioxane, 1,3-dioxolane, 4-methyldioxolane, tetrahydride Ethers such as furan, methyltetrahydrofuran, anisole, phenetol; organic solvents having a nitrile group such as acetonitrile, isobutyronitrile, propionitrile, methoxyacetonitrile; organic solvents having a carbonate group such as ethylene carbonate, propylene carbonate; methylene chloride And organic solvents having a halogenated hydrocarbon group such as chloroform; organic solvents having a hydrocarbon group such as n-pentane, cyclohexane, n-hexane, benzene, toluene and xylene.

In two types of solvents having different solubilities, the difference in solubility is preferably 100 μg / solvent 100 g to 90 g / solvent 100 g, more preferably 1 mg / solvent 100 g to 90 g / solvent 100 g. From the viewpoint of setting the difference in solubility to 100 μg / solvent 100 g to 90 g / solvent 100 g, for example, when performing the mixing step at room temperature (10 ° C. to 30 ° C.), the solvent used in the step of obtaining the solution is N, N-dimethyl. An organic solvent having an amide group such as acetamide or dimethyl sulfoxide, and the solvent used in the mixing step is an organic solvent having a halogenated hydrocarbon group such as methylene chloride or chloroform; n-pentane, cyclohexane, n-hexane, benzene An organic solvent having a hydrocarbon group such as toluene and xylene is preferable.

When semiconductor fine particles are taken out from a dispersion liquid containing semiconductor fine particles, only the semiconductor fine particles can be recovered by performing solid-liquid separation.
Examples of the solid-liquid separation method include a method such as filtration and a method utilizing evaporation of a solvent.

<Second Embodiment of Manufacturing Method of Crystalline Fine Particles of Perovskite Compound>
Hereinafter, a manufacturing method including a step of adding a B component, an X component and an A component to a high-temperature solvent and dissolving them to obtain a solution and a step of cooling the obtained solution will be described.
More specifically, a step of adding a compound containing the B component and the X component and a component A or a compound containing the A component and the X component to a high temperature solvent to obtain a solution, and cooling the obtained solution The manufacturing method including the process to do is mentioned.
In the production method, the semiconductor fine particles according to the present invention can be produced by precipitating the semiconductor fine particles according to the present invention by the difference in solubility due to the temperature difference.

The manufacturing method preferably includes a step of adding a capping ligand from the viewpoint of stably dispersing the semiconductor fine particles.
The manufacturing method preferably includes a step of removing coarse particles by a technique such as centrifugation or filtration after the cooling step. The size of the coarse particles removed by the removal step is preferably 10 μm or more, more preferably 1 μm or more, and further preferably 500 nm or more.

Here, the high-temperature solvent may be a solvent having a temperature at which the compound containing the B component and the X component and the A component or the compound containing the A component and the X component are dissolved. A solvent is preferable, and a solvent at 80 to 400 ° C. is more preferable.
The cooling temperature is preferably −20 to 50 ° C., more preferably −10 to 30 ° C.
The cooling rate is preferably from 0.1 to 1500 ° C./min, more preferably from 10 ° C. to 150 ° C./min.

The solvent used in the production method is not particularly limited as long as it is a solvent that can dissolve the compound containing the B component and the X component and the component A or the compound containing the A component and the X component. , Esters of methyl formate, ethyl formate, propyl formate, pentyl formate, methyl acetate, ethyl acetate, pentyl acetate, etc .; γ-butyrolactone, N-methyl-2-pyrrolidone, acetone, dimethyl ketone, diisobutyl ketone, cyclo Ketones such as pentanone, cyclohexanone, methylcyclohexanone; diethyl ether, methyl-tert-butyl ether, diisopropyl ether, dimethoxymethane, dimethoxyethane, 1,4-dioxane, 1,3-dioxolane, 4-methyldioxolane, tetrahy Ethers such as lofuran, methyltetrahydrofuran, anisole, phenetole; methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, tert-butanol, 1-pentanol, 2-methyl-2-butanol, methoxy Alcohols such as propanol, diacetone alcohol, cyclohexanol, 2-fluoroethanol, 2,2,2-trifluoroethanol, 2,2,3,3-tetrafluoro-1-propanol; ethylene glycol monomethyl ether, ethylene glycol mono Glycol ethers such as ethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, triethylene glycol dimethyl ether; N, N-dimethylform Organic solvents having an amide group such as muamide, acetamide, N, N-dimethylacetamide; organic solvents having a nitrile group such as acetonitrile, isobutyronitrile, propionitrile, methoxyacetonitrile; carbonate groups such as ethylene carbonate and propylene carbonate An organic solvent having a halogenated hydrocarbon group such as methylene chloride and chloroform; an organic solvent having a hydrocarbon group such as n-pentane, cyclohexane, n-hexane, benzene, toluene, xylene; dimethyl sulfoxide, 1-octadecene is mentioned.

As a method for taking out the semiconductor fine particles from the dispersion liquid containing the semiconductor fine particles, a method of collecting only the semiconductor fine particles by performing solid-liquid separation can be mentioned.
Examples of the solid-liquid separation method include a method such as filtration and a method utilizing evaporation of a solvent.

<The manufacturing method of the composition containing (1), (2), and (3)>
(1) Semiconductor fine particles, (2) an organic compound having an amino group, an alkoxy group, and a silicon atom, and (3) a composition comprising at least one selected from the group consisting of a polymerizable compound and a polymer as,
(1) A method of mixing at least one selected from the group consisting of semiconductor fine particles, (2) an organic compound having an amino group, an alkoxy group, and a silicon atom, and (3) a polymerizable compound and a polymer. .
When mixing, it is preferable to mix while stirring from the viewpoint of improving dispersibility.
The mixing temperature is not particularly limited, but is preferably in the range of 0 to 100 ° C., more preferably in the range of 10 to 80 ° C., from the viewpoint of uniform mixing.

The method for producing the composition according to the present invention includes, for example,
(A) (3) A step of obtaining a dispersion by dispersing semiconductor fine particles in at least one selected from the group consisting of a polymerizable compound and a polymer, and (2) an amino group. , An alkoxy group, and a step of mixing an organic compound having a silicon atom,
(B) (3) a step of obtaining a dispersion by dispersing (2) an organic compound having an amino group, an alkoxy group, and a silicon atom in at least one selected from the group consisting of a polymerizable compound and a polymer; The manufacturing method may include a step of mixing the obtained dispersion and (1) semiconductor fine particles,
(C) A mixture of (1) a semiconductor fine particle and (2) an amino group, an alkoxy group, and an organic compound having a silicon atom is dispersed in at least one selected from the group consisting of (3) a polymerizable compound and a polymer. The manufacturing method including a process may be sufficient.

Among the production methods (a) to (c), the production method (a) is preferable from the viewpoint of improving the dispersibility of the semiconductor fine particles. By the above method, the composition according to the present invention is used as a mixture of (1) a dispersion in which semiconductor fine particles are dispersed in (3) and (2) an organic compound having an amino group, an alkoxy group, and a silicon atom. Obtainable.

In the step of obtaining each dispersion included in the production methods (a) to (c), (3) may be added dropwise to (1) and / or (2), and (1) and / or (2) may be added dropwise to (3).
From the viewpoint of enhancing dispersibility, it is preferable to add (1) and / or (2) dropwise to (3).
In each mixing step included in the production methods (a) to (b), (1) or (2) may be added dropwise to the dispersion, or the dispersion is added dropwise to (1) or (2). May be.
From the viewpoint of improving dispersibility, it is preferable to add (1) or (2) dropwise to the dispersion.

When a polymer is employed as the organic compound (3), the polymer may be a polymer dissolved in a solvent.

The solvent in which the polymer is dissolved is not particularly limited as long as it is a solvent that can dissolve the resin (polymer), but is preferably a solvent in which the semiconductor fine particles according to the present invention are difficult to dissolve.
Examples of the solvent in which the above resin is dissolved include, for example, esters such as methyl formate, ethyl formate, propyl formate, pentyl formate, methyl acetate, ethyl acetate, pentyl acetate; γ-butyrolactone, N-methyl- Ketones such as 2-pyrrolidone, acetone, dimethyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methylcyclohexanone; diethyl ether, methyl-tert-butyl ether, diisopropyl ether, dimethoxymethane, dimethoxyethane, 1,4-dioxane, 1, Ethers such as 3-dioxolane, 4-methyldioxolane, tetrahydrofuran, methyltetrahydrofuran, anisole, phenetole; methanol, ethanol, 1-propanol, 2-pro 1-butanol, 2-butanol, tert-butanol, 1-pentanol, 2-methyl-2-butanol, methoxypropanol, diacetone alcohol, cyclohexanol, 2-fluoroethanol, 2,2,2-trifluoro Alcohols such as ethanol and 2,2,3,3-tetrafluoro-1-propanol; glycols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, and triethylene glycol dimethyl ether Ether; organic solvent having an amide group such as N, N-dimethylformamide, acetamide, N, N-dimethylacetamide; acetonitrile, isobutyronitrile, propio Organic solvents having a nitrile group such as nitrile and methoxyacetonitrile; organic solvents having a carbonate group such as ethylene carbonate and propylene carbonate; organic solvents having a halogenated hydrocarbon group such as methylene chloride and chloroform; n-pentane, cyclohexane, Organic solvents having hydrocarbon groups such as n-hexane, benzene, toluene, xylene; dimethyl sulfoxide.

Among them, esters such as methyl formate, ethyl formate, propyl formate, pentyl formate, methyl acetate, ethyl acetate, pentyl acetate; γ-butyrolactone, acetone, dimethyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methylcyclohexanone Ketones such as diethyl ether, methyl-tert-butyl ether, diisopropyl ether, dimethoxymethane, dimethoxyethane, 1,4-dioxane, 1,3-dioxolane, 4-methyldioxolane, tetrahydrofuran, methyltetrahydrofuran, anisole, phenetol , An organic solvent having a nitrile group such as acetonitrile, isobutyronitrile, propionitrile, methoxyacetonitrile; Carbonate organic solvents such as carbonate and propylene carbonate; organic solvents having halogenated hydrocarbon groups such as methylene chloride and chloroform; hydrocarbon groups such as n-pentane, cyclohexane, n-hexane, benzene, toluene and xylene An organic solvent is preferable because it has low polarity and is unlikely to dissolve the perovskite compound according to the present invention, and is preferably an organic solvent having a halogenated hydrocarbon group such as methylene chloride or chloroform; n-pentane, cyclohexane, n-hexane, An organic solvent having a hydrocarbon group such as benzene, toluene or xylene is more preferable.

<The manufacturing method of the composition containing (1), (2), (3), and (4)>
(1) semiconductor fine particles, (2) an organic compound having an amino group, an alkoxy group, and a silicon atom, (3) at least one selected from the group consisting of a polymerizable compound and a polymer, and (4) ammonia, an amine And a method for producing a composition comprising at least one selected from the group consisting of carboxylic acids, and salts or ions thereof,
(4) The composition comprising (1), (2), and (3) described above, except that at least one selected from the group consisting of ammonia, amine, carboxylic acid, and salts or ions thereof is added. It can be set as the method similar to the manufacturing method of a thing.
(4) At least one selected from the group consisting of ammonia, amine, and carboxylic acid, and salts or ions thereof,
Any of the steps included in the above-described method (1) included in the method for manufacturing semiconductor fine particles and included in the method for manufacturing a composition including the above-described (1), (2), and (3). It may be added in the step.
(4) At least one selected from the group consisting of ammonia, amine, carboxylic acid, and salts or ions thereof is included in (1) the method for producing semiconductor fine particles from the viewpoint of enhancing the dispersibility of the semiconductor fine particles. It is preferable to add at any step. Thereby, for example, (4) at least one selected from the group consisting of (4) ammonia, amines, carboxylic acids, and salts or ions thereof, (1) semiconductor fine particles, (3) polymerizable compounds, and polymers The composition according to the present invention can be obtained as a mixture of a dispersion dispersed in at least one selected from the group consisting of: (2) an organic compound having an amino group, an alkoxy group, and a silicon atom. .

<The manufacturing method of the composition which (1), (2) and (3 ') are included, and the sum total of (1), (2) and (3') is 90 mass% or more>
As a method for producing a composition that includes (1), (2), and (3 ′), and the total of (1), (2), and (3 ′) is 90% by mass or more, for example,
(1) mixing a semiconductor fine particle, (2) an organic compound having an amino group, an alkoxy group, and a silicon atom, and a polymerizable compound;
A step of polymerizing a polymerizable compound, and a production method comprising:
(1) A process comprising a step of mixing semiconductor fine particles, (2) an organic compound having an amino group, an alkoxy group and a silicon atom, and a polymer dissolved in the solvent, and a step of removing the solvent. A method is mentioned.

In the mixing step included in the production method, (1) semiconductor fine particles, (2) an organic compound having an amino group, an alkoxy group, and a silicon atom, and (3) a polymerizable compound and a polymer, which have already been described. The mixing method similar to the manufacturing method of the composition containing at least 1 sort (s) chosen from the group which consists of can be used.
The manufacturing method is, for example,
(A1) In the polymerizable compound, (1) a step of dispersing semiconductor fine particles to obtain a dispersion, and the obtained dispersion and (2) an organic compound having an amino group, an alkoxy group, and a silicon atom are mixed. A production method comprising a step and a step of polymerizing a polymerizable compound,
(A2) (1) Step of dispersing semiconductor fine particles in a polymer dissolved in a solvent to obtain a dispersion, and (2) Organic having an amino group, an alkoxy group, and a silicon atom. It may be a production method comprising a step of mixing a compound and a step of removing the solvent,
(B1) In the polymerizable compound, (2) an organic compound having an amino group, an alkoxy group, and a silicon atom is dispersed to obtain a dispersion, and the obtained dispersion is mixed with (1) semiconductor fine particles. And a process comprising polymerizing a polymerizable compound,
(B2) A step of obtaining a dispersion by dispersing (2) an organic compound having an amino group, an alkoxy group, and a silicon atom in a polymer dissolved in a solvent, and the obtained dispersion, (1) The method may include a step of mixing the semiconductor fine particles and a step of removing the solvent,
(C1) Production comprising (1) semiconductor fine particles and (2) a step of dispersing a mixture of an organic compound having an amino group, an alkoxy group, and a silicon atom, and a step of polymerizing the polymerizable compound in the polymerizable compound. It may be a method.
(C2) in the polymer dissolved in the solvent, (1) a step of dispersing the semiconductor fine particles and (2) a mixture of an organic compound having an amino group, an alkoxy group, and a silicon atom, a step of removing the solvent, The manufacturing method containing this may be sufficient.

The step of removing the solvent included in the production method may be a step of standing at room temperature and natural drying, or a step of evaporating the solvent by vacuum drying or heating using a vacuum dryer. Also good.
For example, the solvent can be removed by drying at 0 to 300 ° C. for 1 minute to 7 days.

The step of polymerizing the polymerizable compound included in the production method can be performed 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) semiconductor fine particles, (2) an organic compound having an amino group, an alkoxy group, and a silicon atom, and a polymerizable compound, By making it generate | occur | produce, a polymerization reaction can be advanced.
The radical polymerization initiator is not particularly limited, and examples thereof include a photo radical polymerization initiator.
Examples of the photo radical polymerization initiator include bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide.

<Production of a composition comprising (1), (2), (3 ′) and (4), wherein the total of (1), (2), (3 ′) and (4) is 90% by mass or more Method>
(1) Semiconductor fine particles, (2) an organic compound having an amino group, an alkoxy group, and a silicon atom, (3 ′) a polymer, (4) ammonia, an amine, a carboxylic acid, and a salt or ion thereof. A method for producing a composition comprising at least one selected from the group consisting of (1), (2), (3 ′) and (4) is 90% by mass or more,
(4) Except for adding at least one selected from the group consisting of ammonia, amine, carboxylic acid, and salts or ions thereof, (1), (2), and (3 ′) already described It is the composition containing, Comprising: It can be set as the method similar to the manufacturing method of the composition whose sum total of (1), (2) and (3 ') is 90 mass% or more.
(4) At least one selected from the group consisting of ammonia, amine, and carboxylic acid, and salts or ions thereof,
The above (1) semiconductor fine particles may be added in any step included in the method for producing semiconductor fine particles, and (1) the semiconductor fine particles described above and (2) an organic compound having an amino group, an alkoxy group, and a silicon atom, In the step of mixing the polymerizable compound, the above-mentioned (1) semiconductor fine particles, (2) the organic compound having an amino group, an alkoxy group, and a silicon atom, and the weight dissolved in the solvent. It may be added in the step of mixing the coalescence.
(5) At least one selected from the group consisting of ammonia, amine, carboxylic acid, and salts or ions thereof is from the viewpoint of enhancing the dispersibility of the semiconductor fine particles (1) Any of the methods included in the method for producing semiconductor fine particles It is preferable to add in the step.

≪Measurement of semiconductor fine particles≫
The amount of semiconductor fine particles contained in the composition according to the present invention is measured using ICP-MS (for example, ELAN DRCII, manufactured by PerkinElmer) and an ion chromatograph.
Measurement is performed after the semiconductor fine particles are dissolved using a good solvent such as N, N-dimethylformamide.

≪Measurement of quantum yield≫
The quantum yield of the composition containing the semiconductor fine particles according to the present invention is measured using an absolute PL quantum yield measuring apparatus (for example, product name C9920-02, manufactured by Hamamatsu Photonics) at an excitation light of 450 nm, room temperature, and in the atmosphere. To do.

(1) In a composition comprising semiconductor fine particles and (2) an organic compound having an amino group, an alkoxy group and a silicon atom, and further comprising (3) a polymerizable compound and at least one selected from the group consisting of polymers. Is measured by adjusting the mixing ratio so that the concentration of the semiconductor fine particles contained in the composition is 1000 μg / mL.

In the composition of the present embodiment, the quantum yield measured by the above measuring method may be 32% or more, 40% or more, 50% or more, 60% It may be more than 70% or more.
In the composition of the present embodiment, the quantum yield measured by the above measurement method may be 100% or less, may be 95% or less, may be 90% or less, and may be 80%. It may be the following.
The above upper limit value and lower limit value can be arbitrarily combined.
As one aspect of the present invention, the composition of the present embodiment preferably has a quantum yield measured by the measurement method of 32% or more and 100% or less, and 40% or more and 100% or less. Is more preferably 50% or more and 100% or less, and particularly preferably 70% or more and 100 or less.
As another aspect of the present invention, in the composition of the present embodiment, the quantum yield measured by the measurement method is preferably 32% or more and 95% or less, and 40% or more and 90% or less. Is more preferable, and 50% or more and 80% or less is still more preferable. The quantum yield may be 60% or more and 80% or less, or 70% or more and 80% or less.

≪Evaluation of thermal durability≫
A thermal durability test is performed in which the composition according to the present invention is stored in an oven made constant at a temperature of 60 ° C., and the quantum yield is measured before and after the test. The test piece has a thickness of 100 μm and 1 cm × 1 cm.
The thermal durability can be measured as a value of (quantum yield after thermal durability test for n days) / (quantum yield before thermal durability test).

The composition of this embodiment may have a thermal durability after a 5-day thermal durability test measured by the measurement method described above of 0.4 or more, or 0.6 or more, It may be 0.8 or more.
The composition of the present embodiment may have a heat durability after a 5-day heat durability test measured by the above measurement method of 1.0 or less, or 0.95 or less, It may be 0.9 or less.
As one aspect of the present invention, the composition of the present embodiment has a thermal durability of 0.4 or more and 1.0 or less after a 5-day thermal durability test measured by the measurement method. Preferably, it is 0.6 or more and 1.0 or less, and more preferably 0.8 or more and 1.0 or less.
As another aspect of the present invention, the composition of the present embodiment has a thermal durability of 0.4 or more and 0.95 or less after a 5-day thermal durability test measured by the measurement method. Preferably, it is 0.6 or more and 0.95 or less, more preferably 0.8 or more and 0.9 or less.
The composition of the present embodiment may have a thermal durability after a 7-day thermal durability test measured by the measurement method described above of 0.4 or more, or 0.6 or more, It may be 0.8 or more, or 0.9 or more.
In the composition of the present embodiment, the heat durability after a 7-day heat durability test measured by the above measurement method may be 1.0 or less, or 0.95 or less, It may be 0.9 or less.
As yet another aspect of the present invention, the composition of the present embodiment has a thermal durability after a 7-day thermal durability test measured by the above measurement method of 0.4 or more and 1.0 or less. Is preferably 0.6 or more and 1.0 or less, more preferably 0.8 or more and 1.0, and particularly preferably 0.9 or more and 1.0 or less.
As another aspect of the present invention, the composition of the present embodiment has a thermal durability after a 7-day thermal durability test measured by the measurement method of 0.4 or more and 0.95 or less. Preferably, it is 0.6 or more and 0.95 or less, more preferably 0.8 or more and 0.9 or less. The thermal durability may be 0.9 or more and 0.95 or less.

<Film>
The film according to the present invention includes (1), (2), and (3 ′), and the total content of (1), (2), and (3 ′) is 90 with respect to the total mass of the composition. It is a film made of a composition having a mass% or more.
(1) Semiconductor fine particles (2) Organic compound having amino group, alkoxy group, and silicon atom (3 ′) polymer

The film shape is not particularly limited, and may be a sheet shape, a bar shape or the like. In this specification, the “bar-shaped shape” means, for example, a shape having anisotropy. Examples of the shape having anisotropy include plate-like shapes having different lengths on each side.
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 this specification, the thickness of the film can be obtained by measuring at any three points with a micrometer and calculating the average value.

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

As a method for producing a film, for example, a film formed on a substrate can be obtained by the production methods (i) to (iii) of the production method for a laminated structure described later.

<Laminated structure>
The laminated structure according to the present invention is
Having a plurality of layers, at least one layer being
(1), (2) and (3 ′), wherein the total content of (1), (2) and (3 ′) is 90% by mass or more based on the total mass of the composition It is a laminated structure which is a layer.
(1) Semiconductor fine particles (2) Organic compound having amino group, alkoxy group, and silicon atom (3 ′) polymer

The composition containing (1), (2), and (3 ′) further contains (4) at least one selected from the group consisting of ammonia, amine, and carboxylic acid, and salts or ions thereof. May be.

Among the plurality of layers of the laminated structure, it includes (1), (2), and (3 ′), and the total content of (1), (2), and (3 ′) is the total mass of the composition On the other hand, examples of the layer other than the layer composed of 90% by mass or more include arbitrary layers such as a substrate, a barrier layer, and a light scattering layer.
The shape of the laminated composition is not particularly limited, and may be any shape such as a sheet shape or a bar shape. The laminated composition may be the film of this embodiment.

(substrate)
The layer that the laminated structure according to the present invention may have is not particularly limited, but includes a substrate.
A board | substrate is not specifically limited, A film may be sufficient and a transparent thing is preferable from a viewpoint of taking out light at the time of light emission. As the substrate, for example, a plastic such as polyethylene terephthalate or a known material such as glass can be used.
For example, in the laminated structure, the composition includes (1), (2), and (3 ′), and the total content of (1), (2), and (3 ′) is the total mass of the composition The layer made of the composition of 90% by mass or more with respect to the substrate may be provided on the substrate. The layer may be the film of this embodiment.

FIG. 1 is a cross-sectional view schematically showing the configuration of the laminated structure of the present 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 with a sealing layer 22.
One aspect of the present invention includes 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 sealing. A layered structure having a layer 22, wherein the sealing layer is disposed on a surface of the film 10 that is not in contact with the first substrate 20 and the second substrate 21. This is a laminated structure 1a.

(Barrier layer)
Although there is no restriction | limiting in particular as a layer which the laminated structure which concerns on this invention may have, A barrier layer is mentioned. In order to protect the above-mentioned composition from water vapor in the outside air and air in the atmosphere, a barrier layer may be included.
The barrier layer is not particularly limited, but is preferably a transparent barrier layer from the viewpoint of extracting emitted light. For example, a known barrier layer such as a polymer such as polyethylene terephthalate or a glass film can be applied.

(Light scattering layer)
Although there is no restriction | limiting in particular as a layer which the laminated structure which concerns on this invention may have, A light-scattering layer is mentioned. From the viewpoint of efficiently absorbing the incident light, a light scattering layer may be included.
The light scattering layer is not particularly limited, but a transparent light scattering layer is preferable from the viewpoint of extracting emitted light. For example, a light scattering layer such as silica particles or a known light scattering layer such as an amplification diffusion film is applied. I can do it.

<Method for producing laminated structure>
As a manufacturing method of the laminated structure, for example,
(I) (1) a step of mixing semiconductor fine particles, (2) an organic compound having an amino group, an alkoxy group, and a silicon atom, and a polymer dissolved in a solvent;
Coating the obtained composition on a substrate;
A method for producing a laminated structure including a step of removing the solvent,
(Ii) A composition comprising (1), (2) and (3 ′), wherein the total content of (1), (2) and (3 ′) is relative to the total mass of the composition A method for producing a laminated structure including a step of bonding a composition of 90% by mass or more to a substrate;
(1) Semiconductor fine particles (2) Organic compounds having amino groups, alkoxy groups, and silicon atoms (3 ′) Polymers (iii) (1) Semiconductor fine particles, (2) having amino groups, alkoxy groups, and silicon atoms Mixing an organic compound and a polymerizable compound;
Coating the obtained composition on a substrate;
And a step of polymerizing a polymerizable compound.

The step of mixing and the step of removing the solvent, which are included in the production method of (i),
The step of mixing and the step of polymerizing the polymerizable compound included in the production method of (iii)
Each of the compositions containing (1), (2), and (3 ′), which has already been described, wherein the total content of (1), (2), and (3 ′) is the total mass of the composition It can be set as the process similar to the process included in the manufacturing method of the composition which is 90 mass% or more with respect to this.

The step of coating on the substrate included in the manufacturing methods of (i) and (iii) is not particularly limited, but gravure coating method, bar coating method, printing method, spray method, spin coating method, dip method A known coating method such as a die coating method can be used.

An arbitrary adhesive can be used in the step of bonding to the substrate, which is included in the manufacturing method (ii).
The adhesive is not particularly limited as long as it does not dissolve (1) semiconductor fine particles, and a known adhesive can be used.

The manufacturing method of the laminated structure may be a manufacturing method including a step of further bonding an arbitrary film to the laminated structure obtained in (i) to (iii).
Examples of the film to be bonded include a reflection film and a diffusion film.
Any adhesive can be used in the step of laminating the films.
The above-mentioned adhesive is not particularly limited as long as (1) it does not dissolve the semiconductor fine particles, and a known adhesive can be used.

<Light emitting device>
The light emitting device according to the present invention can be obtained by combining the above composition or the above laminated structure with a light source. The light-emitting device according to the present invention is a device that emits light from the above-mentioned composition by irradiating light emitted from a light source onto the above-described composition installed in the subsequent stage, and extracts the light. The laminated structure in the light emitting device may include layers such as a reflection film, a diffusion film, a brightness enhancement portion, a prism sheet, a light guide plate, and a medium material layer between elements.
One aspect of the present invention is the light emitting device 2 in which the prism sheet 50, the light guide plate 60, the first laminated structure 1a, and the light source 30 are laminated in this order.

(light source)
The light source constituting the light emitting device according to the present invention is not particularly limited, but a light source having an emission wavelength of 600 nm or less is preferable from the viewpoint of emitting the semiconductor fine particles in the composition or the laminated structure, 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.

(Reflective film)
Although there is no restriction | limiting in particular, the light-emitting device concerning this invention can contain the light reflection member for irradiating the light of a light source toward the said composition or the said laminated structure.
The reflective film is not particularly limited, but may include any suitable known material such as a reflector, a film of reflective particles, a reflective metal film, or a reflector.

(Diffusion film)
Although there is no restriction | limiting in particular, the light-emitting device concerning this invention can contain the light-scattering member for diffusing the light of a light source, or the light emitted from the said composition. The diffusion film may include any diffusion film known in the art, such as an amplification diffusion film.

(Brightness enhancement part)
Although there is no restriction | limiting in particular, the light-emitting device concerning this invention can contain the brightness | luminance enhancement part which reflects and returns a part of light toward the direction where the light was transmitted.

(Prism sheet)
The prism sheet typically has a base material portion and a prism portion. In addition, you may abbreviate | omit a base material part according to an adjacent member. The prism sheet can be bonded to an adjacent member via any appropriate adhesive layer (for example, an adhesive layer, an adhesive layer :). The prism sheet includes a plurality of unit prisms that are convex on the opposite side (rear side) to the viewing side. By disposing the convex portion of the prism sheet toward the back side, the light transmitted through the prism sheet is easily collected. In addition, if the convex part of the prism sheet is arranged toward the back side, the light that is reflected without entering the prism sheet is reduced and the brightness is high compared to the case where the convex part is arranged toward the viewing side. Can be obtained.

(Light guide plate)
Any appropriate light guide plate may be used as the light guide plate. For example, a light guide plate in which a lens pattern is formed on the back side and a light guide plate in which a prism shape or the like is formed on the back side and / or the viewing side are used so that light from the lateral direction can be deflected in the thickness direction. .

(Media material layer between elements)
The light emitting device according to the present invention is not particularly limited, but may include a layer made of one or more medium materials on an optical path between adjacent elements (layers). One or more media may include vacuum, air, gas, optical material, adhesive, optical adhesive, glass, polymer, solid, liquid, gel, curable material, optical coupling material, index matching or index mismatch material , Refractive index gradient material, cladding or anti-cladding material, spacer, silica gel, brightness enhancing material, scattering or diffusing material, reflective or anti-reflective material, wavelength selective material, wavelength selective anti-reflective material, color filter, or said Any suitable material known in the art may be included, including but not limited to any suitable material.

Specific examples of the light-emitting device according to the present invention include, for example, those provided with wavelength conversion materials for EL displays and liquid crystal displays.
In particular,
(1) Put the composition of the present invention in a glass tube or the like and seal it, and arrange it between the blue light-emitting diode that is the light source and the light guide plate along the end face (side surface) of the light guide plate, Backlight that converts blue light into green or red light (on-edge type backlight),
(2) A blue film placed on the end face (side face) of the light guide plate by placing the film of the composition according to the present invention into a sheet and sealing it with two barrier films sandwiched between them. A backlight (surface mount type backlight) that converts blue light emitted from the light emitting diodes through the light guide plate to the sheet into green light or red light,
(3) A backlight (on-chip type backlight) that disperses semiconductor fine particles in a resin or the like and is installed in the vicinity of the light emitting portion of the blue light emitting diode, and converts the emitted blue light into green light or red light; And (4) A backlight in which semiconductor fine particles are dispersed in a resist and placed 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 invention, the composition of the present invention is molded and disposed at the subsequent stage of the blue light emitting diode as the light source, and the blue light is converted into green light or red light to generate white light Illumination that emits.

<Method for manufacturing light emitting device>
For example, the manufacturing method including the above-mentioned light source and the process of installing the above-mentioned composition or laminated structure on the optical path of a back | latter stage from a light source is mentioned.

<Display>
As shown in FIG. 2, the display 3 of this embodiment includes a liquid crystal panel 40 and the light-emitting device 2 described above in this order from the viewing side. The light emitting device 2 includes a second laminated structure 1b and a light source 30. In the second laminated structure 1b, the first laminated structure 1a described above further includes a prism sheet 50 and a light guide plate 60. The liquid crystal panel typically includes a liquid crystal cell, a viewing side polarizing plate disposed on the viewing side of the liquid crystal cell, and a back side polarizing plate disposed on the back side of the liquid crystal cell. The display may further include any appropriate other member.
One aspect of the present invention is the liquid crystal display 3 in which the liquid crystal panel 40, the prism sheet 50, the light guide plate 60, the first laminated structure 1a, and the 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 disposed on the viewing side of the liquid crystal cell, and a back side polarizing plate disposed on the back side of the liquid crystal cell. The viewing-side polarizing plate and the back-side polarizing plate can be arranged so that their absorption axes are substantially orthogonal or parallel.

(Liquid crystal cell)
The liquid crystal cell includes a pair of substrates and a liquid crystal layer as a display medium sandwiched between the substrates. In a general configuration, a color filter and a black matrix are provided on one substrate, a switching element that controls the electro-optical characteristics of the liquid crystal on the other substrate, and a scanning line that supplies a gate signal to the switching element. In addition, a signal line for supplying a source signal, a pixel electrode, and a counter electrode are provided. The distance between the substrates (cell gap) can be controlled by a spacer or the like. For example, an alignment film made of polyimide can be provided on the side of the substrate in contact with the liquid crystal layer.

(Polarizer)
The polarizing plate typically includes a polarizer and protective layers disposed on both sides of the polarizer. The polarizer is typically an absorptive polarizer.
Any appropriate polarizer is used as the polarizer. For example, dichroic substances such as iodine and dichroic dyes are adsorbed on hydrophilic polymer films such as polyvinyl alcohol films, partially formalized polyvinyl alcohol films, and ethylene / vinyl acetate copolymer partially saponified films. And polyene-based oriented films such as a uniaxially stretched product, a polyvinyl alcohol dehydrated product and a polyvinyl chloride dehydrochlorinated product. Among these, a polarizer obtained by adsorbing a dichroic substance such as iodine on a polyvinyl alcohol film and uniaxially stretching is particularly preferable because of its high polarization dichroic ratio.

Examples of the use of the composition according to the present invention include a wavelength conversion material for a laser diode.
<LED>
The composition according to the present invention can be used, for example, as a material for a light emitting layer of an LED.
As an LED including the composition according to the present invention, for example, the composition according to the present invention and conductive particles such as ZnS are mixed and laminated in a film shape, an n-type transport layer is laminated on one side, and the other side is laminated. It has a structure laminated with a p-type transport layer, and by passing an electric current, the holes of the p-type semiconductor and the electrons of the n-type semiconductor cancel the charge in the semiconductor fine particles contained in the composition of the bonding surface. There is a method of emitting light.

<Solar cell>
The composition according to the present invention can be used as an electron transporting material contained in the active layer of a solar cell.
The configuration of the solar cell is not particularly limited. For example, a fluorine-doped tin oxide (FTO) substrate, a titanium oxide dense layer, a porous aluminum oxide layer, an active layer containing the composition according to the present invention, A hole transport layer such as 2 ′, 7,7′-tetrakis- (N, N′-di-p-methoxyphenylamine) -9,9′-spirobifluorene (Spiro-OMeTAD) and a silver (Ag) electrode are arranged in this order. The solar cell which has in. Is mentioned.
The titanium oxide dense layer has an electron transport function, an effect of suppressing FTO roughness, and a function of suppressing reverse electron transfer.
The porous aluminum oxide layer has a function of improving light absorption efficiency.
The composition according to the present invention contained in the active layer plays a role of charge separation and electron transport.

The technical scope of the present invention is not limited to the above-described embodiment, 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.

(Synthesis of composition)
[Example 1]
Cesium carbonate 0.814g, 1-octadecene solvent 40mL and oleic acid 2.5mL 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. The mixture was stirred with a magnetic stirrer and heated at 120 ° C. for 1 hour while flowing nitrogen, and then 2 mL of oleic acid and 2 mL of oleylamine were added. After raising the temperature to 160 ° C., 1.6 mL of the above cesium carbonate solution was added. After the addition, the reaction vessel was immersed in ice water to lower the temperature to room temperature.
Next, the precipitate was separated by centrifuging the dispersion at 10,000 rpm for 5 minutes to obtain precipitated semiconductor fine particles.
When the X-ray diffraction pattern of the semiconductor fine particles was measured with an X-ray diffraction measurement device (XRD, Cu Kα ray, X′pert PRO MPD, manufactured by Spectris Co., Ltd.), (hkl) = (001) at a position of 2θ = 14 °. It has a peak derived from it and was confirmed to have a three-dimensional perovskite crystal structure.
The average ferret diameter of the perovskite compound observed by TEM (manufactured by JEOL Ltd., JEM-2200FS) was 11 nm.
After dispersing the semiconductor fine particles in 5 mL of toluene, 500 μL of the dispersion was taken and redispersed in 4.5 mL of toluene to obtain a dispersion containing the semiconductor fine particles and the solvent. The concentration of the perovskite compound measured by ICP-MS and ion chromatography was 1500 ppm (μg / g).
Next, after being mixed with toluene so that the methacrylic resin (PMMA, manufactured by Sumitomo Chemical Co., Ltd., Sumipex methacrylic resin, MH, molecular weight of about 120,000, specific gravity 1.2 g / ml) becomes 16.5% by mass, By heating for 3 hours, a solution in which the polymer was dissolved was obtained. After mixing 0.15 g of the above dispersion containing the semiconductor fine particles and the solvent and 0.913 g of the polymer-dissolved solution, an aluminum cup (with a molar ratio of 3-Aminopropyltrimethoxysilane / Pb = 2.55) ( (4.5φcm).
Toluene was evaporated by natural drying to obtain a composition having a perovskite compound concentration of 1000 μg / mL. The composition was cut to a size of 1 cm × 1 cm.

(Measurement of semiconductor fine particles)
The concentration of the semiconductor fine particles in the compositions obtained in the examples and comparative examples was determined by adding N, N-dimethylformamide to the dispersion containing the semiconductor fine particles and the solvent obtained by redispersion, respectively. After the fine particles were dissolved, measurement was performed using ICP-MS (ELAN DRCII, manufactured by Perkin Elmer) and an ion chromatograph.

(Quantum yield measurement)
The quantum yield of the compositions obtained in Examples 1 to 6 and Comparative Example 1 was measured using an absolute PL quantum yield measuring apparatus (manufactured by Hamamatsu Photonics, trade name C9920-02, excitation light 450 nm, room temperature, in the atmosphere). And measured.

(Evaluation of thermal durability)
The compositions obtained in Examples 1 to 6 and Comparative Example 1 were placed in an oven kept constant at a temperature of 60 ° C., and the quantum yield was measured after 5 days or 7 days.

The quantum yield before the heat durability test of the composition obtained in Example 1 was 62%, and the quantum yield after 5 days of the heat durability test was 28%. The value of (quantum yield after 5 days of thermal durability test) / (quantum yield before thermal durability test) was 0.45.

[Example 2]
A composition was obtained in the same manner as in Example 1 except that 3-Aminopropyltrimethoxysilane / Pb = 4.25.
The quantum yield before the heat endurance test was 66%, and the quantum yield after 5 days of the heat endurance test was 28%. The value of (quantum yield after 5 days of thermal durability test) / (quantum yield before thermal durability test) was 0.42.

[Example 3]
A composition was obtained in the same manner as in Example 1 except that 3-Aminopropyltrimethoxysilane / Pb = 8.51.
The quantum yield before the heat durability test was 72%, and the quantum yield after 5 days of the heat durability test was 61%. The value of (quantum yield after 5 days of thermal durability test) / (quantum yield before thermal durability test) was 0.85.

[Example 4]
A composition was obtained in the same manner as in Example 1 except that 3-Aminopropyltrimethoxysilane / Pb = 17.0.
The quantum yield before the heat endurance test was 72%, and the quantum yield after 7 days of the heat endurance test was 65%.

[Example 5]
A composition was obtained in the same manner as in Example 1 except that 3-Aminopropyltrimethoxysilane / Pb = 25.5.
The quantum yield before the heat endurance test was 79%, and the quantum yield after 7 days of the heat endurance test was 66%.

[Example 6]
A composition was obtained in the same manner as in Example 1 except that 3-Aminopropyltrimethoxysilane / Pb = 42.5.
The quantum yield before the heat endurance test was 79%, and the quantum yield after 7 days of the heat endurance test was 67%.

[Comparative Example 1]
Cesium carbonate 0.814g, 1-octadecene solvent 40mL and oleic acid 2.5mL 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. The mixture was stirred with a magnetic stirrer and heated at 120 ° C. for 1 hour while flowing nitrogen, and then 2 mL of oleic acid and 2 mL of oleylamine were added. After raising the temperature to 160 ° C., 1.6 mL of the above cesium carbonate solution was added. After the addition, the reaction vessel was immersed in ice water to lower the temperature to room temperature.
Next, the precipitate was separated by centrifuging the dispersion at 10,000 rpm for 5 minutes to obtain precipitated semiconductor fine particles.
When the X-ray diffraction pattern of the semiconductor fine particles was measured with an X-ray diffraction measurement device (XRD, Cu Kα ray, X′pert PRO MPD, manufactured by Spectris Co., Ltd.), (hkl) = (001) at a position of 2θ = 14 °. It has a peak derived from it and was confirmed to have a three-dimensional perovskite crystal structure.
The average ferret diameter of the perovskite compound observed by TEM (manufactured by JEOL Ltd., JEM-2200FS) was 11 nm.
After dispersing the semiconductor fine particles in 5 mL of toluene, 500 μL of the dispersion was taken and redispersed in 4.5 mL of toluene to obtain a dispersion containing the semiconductor fine particles and the solvent. The concentration of the perovskite compound measured by ICP-MS and ion chromatography was 1000 μg / mL.
Next, after being mixed with toluene so that the methacrylic resin (PMMA, manufactured by Sumitomo Chemical Co., Ltd., Sumipex methacrylic resin, MH, molecular weight of about 120,000, specific gravity 1.2 g / ml) becomes 16.5% by mass, By heating for 3 hours, a solution in which the polymer was dissolved was obtained. A dispersion containing 0.15 g of the above-mentioned semiconductor fine particles and solvent and 0.913 g of a solution in which the polymer was dissolved were mixed in an aluminum cup (4.5 φcm).
Toluene was evaporated by natural drying to obtain a composition having a perovskite compound concentration of 1000 μg / mL. The composition was cut to a size of 1 cm × 1 cm.
The quantum yield before the heat endurance test was 27%, the quantum yield after 5 days of the heat endurance test was 8%, and the quantum yield after 7 days of the heat endurance test was 0%. The value of (quantum yield after 5 days of thermal durability test) / (quantum yield before thermal durability test) was 0.30.

[Comparative Example 2]
Cesium carbonate 0.814g, 1-octadecene solvent 40mL and oleic acid 2.5mL 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. The mixture was stirred with a magnetic stirrer and heated at 120 ° C. for 1 hour while flowing nitrogen, and then 2 mL of oleic acid and 2 mL of oleylamine were added. After raising the temperature to 160 ° C., 1.6 mL of the above cesium carbonate solution was added. After the addition, the reaction vessel was immersed in ice water to lower the temperature to room temperature.
Next, the precipitate was separated by centrifuging the dispersion at 10,000 rpm for 5 minutes to obtain precipitated semiconductor fine particles.
When the X-ray diffraction pattern of the semiconductor fine particles was measured with an X-ray diffraction measurement device (XRD, Cu Kα ray, X′pert PRO MPD, manufactured by Spectris Co., Ltd.), (hkl) = (001) at a position of 2θ = 14 °. It has a peak derived from it and was confirmed to have a three-dimensional perovskite crystal structure.
The average ferret diameter of the perovskite compound observed by TEM (manufactured by JEOL Ltd., JEM-2200FS) was 11 nm.
After dispersing the semiconductor fine particles in 5 mL of toluene, 500 μL of the dispersion was taken and redispersed in 4.5 mL of toluene to obtain a dispersion containing the semiconductor fine particles and the solvent. The concentration of the perovskite compound measured by ICP-MS and ion chromatography was 1000 μg / mL.
Next, after being mixed with toluene so that the methacrylic resin (PMMA, manufactured by Sumitomo Chemical Co., Ltd., Sumipex methacrylic resin, MH, molecular weight of about 120,000, specific gravity 1.2 g / ml) becomes 16.5% by mass, By heating for 3 hours, a solution in which the polymer was dissolved was obtained. After mixing 0.15 g of the above-mentioned dispersion containing semiconductor fine particles and solvent and 0.913 g of the solution in which the polymer is dissolved, an aluminum cup (4.4) is added so that the molar ratio is Tetramethoxysilane / Pb = 10.1. Mixed in 5 cm).
Toluene was evaporated by natural drying to obtain a composition having a perovskite compound concentration of 1000 μg / mL. The composition was cut to a size of 1 cm × 1 cm.
The quantum yield before the heat endurance test was 29%, the quantum yield after 5 days of the heat endurance test was 7%, and the quantum yield after 7 days of the heat endurance test was 0%. The value of (quantum yield after 5 days of thermal durability test) / (quantum yield before thermal durability test) was 0.24.

Table 1 below describes the composition, quantum yield (%), and thermal durability of the compositions of Examples 1 to 6 and Comparative Examples 1 and 2. In Table 1, the organic compound / Pb having an amino group, an alkoxy group, and a silicon atom represents a molar ratio obtained by dividing the amount of the organic compound having an amino group, an alkoxy group, and a silicon atom by the amount of Pb.
The thermal durability was evaluated by the value of (quantum yield after n-day thermal durability test) / (quantum yield before thermal durability test).
FIG. 3 shows the results of Examples 1 to 3.

From the above results, it can be seen that the compositions of Examples 1 to 6 to which the present invention is applied have superior thermal durability compared to the compositions of Comparative Examples 1 to 2 to which the present invention is not applied. It could be confirmed.

[Reference Example 1]
The composition described in Examples 1 to 6 is put in a glass tube or the like and sealed, and then placed between a blue light emitting diode as a light source and a light guide plate, so that the blue light of the blue light emitting diode is emitted. Manufactures backlights that can be converted to green or red light.

[Reference Example 2]
A resin composition can be obtained by forming the composition described in Examples 1 to 6 into a sheet, and by placing a sealed film sandwiched between two barrier films on a light guide plate, A backlight capable of converting blue light emitted from the blue light emitting diode placed on the end surface (side surface) of the light guide plate through the light guide plate to the sheet into green light or red light is manufactured.

[Reference Example 3]
By installing the compositions described in Examples 1 to 6 in the vicinity of the light emitting portion of the blue light emitting diode, a backlight capable of converting the blue light irradiated to 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 6 and the resist and then removing the solvent. A backlight capable of converting the blue light of the light source into green light or red light by placing the obtained wavelength conversion material between the blue light emitting diode as the light source and the light guide plate or after the OLED as the light source. To manufacture.

[Reference Example 5]
The composition described in Examples 1 to 6 is mixed with conductive particles such as ZnS to form a film, an n-type transport layer is stacked on one side, and a p-type transport layer is stacked on the other side to obtain an LED. . By passing an electric current, holes in the p-type semiconductor and electrons in the n-type semiconductor can be made to emit light by canceling charges in the semiconductor fine particles on the junction surface.

[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 compositions described in Examples 1 to 6 are laminated thereon. Then, after removing the solvent, a hole transport layer such as 2,2-, 7,7-tetrakis- (N, N-di-p-methoxyphenylamine) 9,9-spirobifluorene (Spiro-OMeTAD) is laminated thereon. Then, a silver (Ag) layer is laminated thereon to produce a solar cell.

[Reference Example 7]
The resin composition containing the composition according to the present invention can be obtained by mixing the composition described in Examples 1 to 6 and the resin, and then removing the solvent and molding, and this can be obtained after the blue light-emitting diode. The laser diode illumination that emits white light by converting blue light emitted from the blue light emitting diode to the resin molded body into green light or red light is manufactured.

ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to provide the composition using a highly heat-resistant composition, the film which consists of the said composition, the laminated structure containing the said composition, and the display using the said composition.
Therefore, the composition of the present invention, the film comprising the composition, the laminated structure containing the composition, and the display using the composition can be suitably used in light emitting applications.

DESCRIPTION OF SYMBOLS 1a ... 1st laminated structure, 1b ... 2nd laminated structure, 10 ... Film, 20 ... 1st board | substrate, 21 ... 2nd board | 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 (1), (2), and (3) and having luminescence.
(1) Semiconductor fine particles (2) Organic compounds having amino groups, alkoxy groups, and silicon atoms (3) At least one selected from the group consisting of polymerizable compounds and polymers
The composition according to claim 1, wherein (1) is a fine particle of a perovskite compound having A, B, and X as constituent components.
A is a component located at each vertex of a hexahedron centered on B in the perovskite crystal structure, and is a monovalent cation.
X represents a component located at each vertex of an octahedron centered on B in the perovskite crystal structure, and is one or more anions selected from the group consisting of halide ions and thiocyanate ions.
B is a component located at the center of a hexahedron that arranges A at the apex and an octahedron that arranges X at the apex in the perovskite crystal structure, and is a metal ion.
The composition according to claim 1 or 2, wherein the (1) is a mixture of the dispersion dispersed in the (3) and the (2).
The composition according to any one of claims 1 to 3, further comprising (4) at least one selected from the group consisting of ammonia, amine, carboxylic acid, and salts or ions thereof.
A composition comprising (1), (2) and (3 ′), wherein the total content of (1), (2) and (3 ′) is 90% by mass relative to the total mass of the composition A composition that is above.
(1) Semiconductor fine particles (2) Organic compound having amino group, alkoxy group, and silicon atom (3 ′) polymer
The composition according to claim 5, further comprising (4) at least one selected from the group consisting of ammonia, amine, carboxylic acid, and salts or ions thereof.
A film comprising the composition according to claim 5 or 6.
A laminated structure having a plurality of layers, at least one of which is a layer made of the composition according to claim 5 or 6.
A light emitting device comprising the laminated structure according to claim 8.
A display comprising the laminated structure according to claim 8.
(1) is dispersed in (3) to obtain a dispersion;
The manufacturing method of the composition which has luminescent property including the process of mixing the obtained dispersion and (2).
(1) Semiconductor fine particles (2) Organic compounds having amino groups, alkoxy groups, and silicon atoms (3) At least one selected from the group consisting of polymerizable compounds and polymers