TWI750285B - Composition, film, laminated structure, light emitting device, and display - Google Patents

Abstract

The present invention relates to a compound comprising (1), (2), and (3), and having luminescent properties, wherein (1) is semiconductor fine particles, (2) is an organic compound having a mercapto group, and (3) is at least one of the group consisting of polymerizable compound and polymer. The (1) is preferably fine particles of a compound having a perovskite type crystal structure, said compound comprising A ions, B ions, X ions, wherein: the A ions are monovalent cations, and from hexahedrons in the perovskite type crystal structure with the A ions being located respective vertexes thereof while the B ions being located at respective centers thereof; the B ions are metal ions; the X ions are at least one type of anions selected from the group consisting of halogen ions and thiocyanate ions, and form octahedrons in the perovskite type crystal structure with the X ions being position at respective vertexes thereof while the B ions being located at respective centers thereof.

Description

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

The present invention relates to compositions, films, laminated structures, light-emitting devices, and displays.

This application claims priority based on Japanese Patent Application No. 2016-250172 for which it applied to Japan on December 22, 2016, the content of which is incorporated herein by reference.

In recent years, interest in the light-emitting properties of semiconductor materials has continued to increase.

For example, under room temperature conditions, a composition having a strong luminescence intensity in the spectral range from ultraviolet to red has been reported (Non-Patent Document 1).

[Prior Art Literature] [Patent Literature]

[Non-Patent Document 1] M.Era, A. Shimizu and M. Nagano, Rep. Prog. Polym. Phys. Jpn., 42, 473-474 (1999)

However, when the composition described in the above-mentioned Non-Patent Document 1 is used as a light-emitting material, it is required to further improve the quantum yield.

The present invention has been made in view of the above-mentioned problems, and an object of the present invention is to provide a composition, a film, a laminated structure, a light-emitting device, and a display having a high quantum yield including semiconductor fine particles.

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

That is, the present invention includes the inventions of the following [1] to [9].

[1] A luminescent composition comprising (1), (2) and (3); (1) semiconductor fine particles, (2) an organic compound having a hydrogen thiol group, and (3) selected from polymerizable compounds and at least one of the group consisting of polymers.

[2] The composition according to the above item [1], wherein (1) is a fine particle of a perovskite compound containing A, B and X as constituents; A is in a perovskite crystal structure, The component located at each vertex of the hexahedron with B as the center, and is a monovalent cation; X represents the component located at each vertex of the octahedron with B as the center in the perovskite crystal structure, select One or more anions of the group consisting of free halide ions and thiocyanate ions; B is located in the hexahedron with A at the vertex and the 8-face with X at the vertex in the perovskite crystal structure The composition of the center of the body, and is a metal ion.

[3] The composition according to the aforementioned [1] or [2], further comprising (4) at least one selected from the group consisting of ammonia, amines, and carboxylic acids, and salts or ions of these kind.

[4] A composition comprising (1), (2) and (3'), and the total content of (1), (2) and (3') relative to the total mass of the aforementioned composition is 90% by mass or more; (1) semiconductor fine particles, (2) organic compounds having a hydrogen thio group, (3') polymers.

[5] The composition according to the above item [4], further comprising (4) at least one selected from the group consisting of ammonia, amines, and carboxylic acids, and salts or ions thereof.

[6] A film comprising the composition described in the above item [4] or [5].

[7] A laminated structure having a plurality of layers, and at least one layer is composed of the composition described in the aforementioned [4] or [5].

[8] A light-emitting device including the laminated structure described in the above item [7].

[9] A display including the laminated structure described in the above item [7].

According to the present invention, it is possible to provide a composition, a film, a laminated structure, a light-emitting device, and a display having a high quantum yield containing semiconductor fine particles.

1a‧‧‧The first laminated structure

1b‧‧‧Second layered structure

2‧‧‧Light-emitting device

3‧‧‧Display

10‧‧‧Film

20‧‧‧First substrate

21‧‧‧Second board

22‧‧‧Sealing layer

30‧‧‧Light source

40‧‧‧LCD panel

50‧‧‧Diamond Tablets

60‧‧‧Light guide plate

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

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

Fig. 3 is a graph showing the results of the quantum yield of the composition according to the present invention obtained in Examples.

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

<Composition>

The composition of the present invention is luminescent. The so-called "luminescence" refers to the property of emitting light. The luminescent property is preferably the property of emitting light by electron excitation, and more preferably the property of emitting light by the excitation of electrons generated by the excitation light. The wavelength of the excitation light is, for example, 200 nm to 800 nm, 250 nm to 700 nm, or 300 nm to 600 nm.

The composition of the present invention contains (1), (2) and (3).

(1) semiconductor fine particles, (2) an organic compound having a hydrogen thiol group, and (3) at least one selected from the group consisting of a polymerizable compound and a polymer.

The aforementioned composition system may further contain (4) at least one selected from the group consisting of ammonia, amines, carboxylic acids, and salts or ions of these.

Moreover, the said composition system may have other components other than the said (1)-(4).

The other components include, for example, a solvent, some impurities, a compound having an amorphous structure composed of elemental components constituting semiconductor fine particles, and a polymerization initiator.

The content of other components is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 1% by mass or less, based on the total mass of the composition.

As a result of intensive research, the inventors of the present invention found that a composition comprising (1) semiconductor fine particles, (2) an organic compound having a hydrogen thio group, and (3) one or more kinds selected from the group consisting of a polymerizable compound and a polymer can improve the quantum yield.

It is believed that the organic compound of (2) can prevent the electrons trapped by the surface defects of the semiconductor microparticles of (1) from deactivating, and since the electrons are excited, the quantum yield can be improved.

The composition of the present embodiment contains (1), (2) and (3), and the total content of (1), (2) and (3) may be 90% by mass or more relative to the total mass of the composition , may be 95 mass % or more, 99 mass % or more, or 100 mass %.

The composition of the present invention may contain (1), (2) and (3'), and the total content of (1), (2) and (3') may be 90% by mass or more relative to the total mass of the composition composition.

(1) semiconductor fine particles, (2) organic compound having a hydrogen thiol group, (3') polymer.

In the composition of the present embodiment, the total content of (1), (2) and (3') may be 95% by mass or more, 99% by mass or more, or more than the total mass of the above-mentioned composition. 100% by mass.

The present composition may further contain (4) at least one selected from the group consisting of ammonia, amine, carboxylic acid, and salts or ions of these. The components other than (1), (2), (3') and (4) include, for example, the same components as the other components described above.

In the composition of the present embodiment containing (1), (2) and (3), the content of (1) is not particularly limited with respect to the total mass of the composition, but from the viewpoint of difficulty in condensing the semiconductor fine particles, And from the viewpoint of preventing concentration quenching, it is preferably 50 mass % or less, more preferably 1 mass % or less, even more preferably 0.5 mass % or less, and from the viewpoint of obtaining a good quantum yield, 0.0001 mass % % or more is preferable, 0.0005 mass % or more is more preferable, and 0.001 mass % or more is even more preferable.

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

The content of (1) is usually 0.0001 to 50 mass % with respect to the total mass of the composition.

The content of (1) is preferably 0.0001 to 1 mass %, more preferably 0.0005 to 1 mass %, and even more preferably 0.001 to 0.5 mass % relative to the total mass of the composition.

The range related to the preparation of (1) is a composition within the above-mentioned range, and it is preferable that the aggregation of the semiconductor fine particles of (1) is unlikely to occur, and the light-emitting properties are also well exhibited.

In this specification, the content of the semiconductor fine particles in (1) can be measured by, for example, an inductively coupled plasma mass spectrometer (hereinafter, also referred to as ICP-MS) and ion chromatography with respect to the total mass of the composition.

In the composition of the present embodiment containing (1), (2) and (3), the total content of (1) and (2) is not particularly limited with respect to the total mass of the composition, but it is difficult to make From the viewpoint of condensation of semiconductor fine particles and the viewpoint of preventing concentration quenching, it is preferably 60 mass % or less, more preferably 10 mass % or less, even more preferably 2 mass % or less, and particularly preferably 0.2 mass % or less. In addition, from the viewpoint of obtaining a good quantum yield, it is preferably 0.0002 mass % or more, more preferably 0.002 mass % or more, and even more preferably 0.005 mass % or more.

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

The total content of (1) and (2) is usually 0.0002 to 60 mass % with respect to the total mass of the composition.

The total content of (1) and (2) is preferably 0.001 to 10% by mass, more preferably 0.002 to 2% by mass, and even more preferably 0.005 to 0.6% by mass relative to the total mass of the composition.

The ranges related to the blending ratios of (1) and (2) are compositions within the above-mentioned ranges, and are preferable in that the aggregation of the semiconductor fine particles of (1) is unlikely to occur, and the luminescence properties are also well exhibited.

In the composition of the present embodiment containing (1), (2) and (3'), the content of (1) is not particularly limited relative to the total volume of the composition, but from the viewpoint of difficulty in condensing the semiconductor fine particles , and from the viewpoint of preventing concentration quenching, preferably below 100 g/L, more preferably below 10 g/L, even more preferably below 5 g/L, and from the viewpoint of obtaining a good quantum yield, 0.01 g/L or more is more preferable, 0.1 g/L or more is more preferable, and 0.5 g/L or more is still more preferable.

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

Relative to the total volume of the composition, the content of (1) is preferably 0.01 to 100 g/L, more preferably 0.1 to 10 g/L, and even more preferably 0.5 to 5 g/L.

The range related to the blending of (1) is a composition within the above-mentioned range, and is preferable in that the luminescence property is well exhibited.

In this specification, the content of (1) can be measured by, for example, ICP-MS and ion chromatography with respect to the total volume of the composition.

In this specification, the content of (1) can be measured by, for example, ICP-MS and ion chromatography with respect to the total volume of the composition.

When the composition is in the form of a film, the total volume of the composition can be calculated by cutting the film into a length of 1 cm x 1 cm in width, and measuring the thickness in micrometers or the like.

When the composition is liquid, the total volume of the composition can be measured using a graduated cylinder.

When the composition is powder, the total volume of the composition can be calculated by measuring the density of the heavy carrier according to JIS R 93-1-2-3:1999, and dividing the weight of the composition for measurement by the density of the heavy carrier.

In the composition of the present embodiment containing (1), (2) and (3'), the total content of (1) and (2) with respect to the total volume of the composition is not particularly limited, but it is difficult to use From the viewpoint of the condensation of semiconductor fine particles and the viewpoint of preventing concentration quenching, it is preferably 1000 g/L or less, more preferably 500 g/L or less, even more preferably 300 g/L or less, in order to obtain a good quantum yield From the viewpoint, it is preferably 0.02 g/L or more, more preferably 0.2 g/L or more, and even more preferably 0.6 g/L or more.

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

Relative to the total volume of the composition, the total content of (1) and (2) is preferably 0.02 to 1000 g/L, more preferably 0.2 to 500 g/L, still more preferably 0.6 to 300 g/L.

The ranges related to the blending ratios of (1) and (2) are compositions within the above-mentioned ranges, and are preferable in terms of exhibiting good luminescence properties.

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

(1) Semiconductor fine particles

The composition according to the present invention contains (1) semiconductor fine particles, and (1) the semiconductor fine particles are preferably 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.

In the present specification, "dispersed" refers to a state in which the semiconductor fine particles are suspended or suspended in a dispersion medium.

The semiconductor fine particles of the present invention include, for example, fine particles of crystals of group II-VI compound semiconductors, fine particles of crystals of group II-V compound semiconductors, fine particles of crystals of group III-V compound semiconductors, and fine particles of group III-IV compound semiconductors. Microparticles of crystallized semiconductors, microparticles of group III-VI compound semiconductors, microparticles of group IV-VI compound semiconductors, microparticles of transition metal-p-block compound semiconductor crystals, and microparticles of perovskite compounds microparticles, etc.

From the viewpoint of obtaining a good quantum yield, the semiconductor microparticles are preferably crystalline microparticles of a cadmium-containing semiconductor, crystalline microparticles of an indium-containing semiconductor, and microparticles of a perovskite compound. For the point where it is easy to obtain a light emission peak with a full width at half maximum, fine particles of a perovskite compound are more preferable.

At least a part of these semiconductor fine particles may be covered with (2) the organic compound containing a hydrogen sulfide group.

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, more preferably 2 nm or more, and even more preferably 3 nm or more Also, from the viewpoint of making the semiconductor fine particles of the present invention difficult to settle, the average particle size is preferably 10 μm or less, more preferably 1 μm or less, and even more preferably 500 nm or less.

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

The average particle size of the semiconductor fine particles contained in the composition is not particularly limited, but the average particle size is preferably 1 nm or more and 10 μm or less, and preferably 2 nm or more and 1 μm from the viewpoint of making the semiconductor fine particles difficult to settle and maintaining a good crystal structure. The following is more preferable, and 3 nm or more and 500 nm or less are even more preferable.

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 Feret diameter of 20 semiconductor fine particles contained in the composition by TEM or SEM, and calculating the average maximum Feret diameter of the equivalent average value, the aforementioned can be obtained. The average particle size. In this specification, "maximum Feret 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 from the viewpoint of maintaining a good crystal structure, the median diameter (D50) is preferably 3 nm or more, more preferably 4 nm or more, and even more preferably 5 nm or more Furthermore, from the viewpoint of making the semiconductor fine particles of the present invention difficult to settle, the median diameter (D50) is preferably 5 μm or less, more preferably 500 nm or less, and even more preferably 100 nm or less.

Another aspect of the present embodiment is that the median diameter (D50) of 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, still more preferably 5 nm to 100 nm .

In this specification, the particle size distribution of the semiconductor fine particles contained in the composition can be measured by, for example, TEM and SEM. Specifically, the maximum Feret diameter of 20 semiconductor fine particles contained in the composition can be observed by TEM or SEM, and the median diameter (D50) can be determined from the equal distribution.

(fine particles of crystals of group II-VI compound semiconductors)

A group II-VI compound semiconductor means an element of group 2 or group 12 and an element of group 16 of the periodic table.

In addition, in this specification, "periodic table" means a long-period type periodic table.

Examples of the binary group II-VI compound semiconductor system include CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, HgS, HgSe, or HgTe.

Binary system II-VI compound semiconductors containing elements selected from Group 2 of the periodic table (first element) and elements selected from Group 16 of the periodic table (second element) include, for example, MgS, MgSe, MgTe, CaS, CaSe, CaTe, SrS, SrSe, SrTe, BaS, BaSe, or BaTe.

A group II-VI compound semiconductor system containing an element selected from Group 2 of the periodic table (the first element) and an element selected from Group 16 of the periodic table (the second element) may contain an element selected from Group 2 of the periodic table ( 1st element) 1 type and 2 types selected from group 16 elements (second element) of the periodic table of ternary system II-VI compound semiconductors, may contain elements selected from group 2 of the periodic table (the first element ) 2 types, and 1 type of ternary system II-VI compound semiconductor selected from Group 16 elements (second element) of the periodic table, may contain 2 types of elements selected from Group 2 (first element) of the periodic table , and a quaternary group II-VI compound semiconductor selected from two types of elements of group 16 (the second element) of the periodic table.

Binary system II-VI compound semiconductors containing elements selected from Group 12 of the periodic table (first element) and elements selected from Group 16 of the periodic table (second element) include, for example, ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, HgS, HgSe, or HgTe.

A group II-VI compound semiconductor containing an element selected from Group 12 of the Periodic Table (the first element) and an element selected from Group 16 of the Periodic Table (the second element) may contain an element selected from Group 12 of the Periodic Table (1st element) 1 type, and 2 types selected from group 16 elements of the periodic table (the second element) ternary system II-VI group compound semiconductor, may contain elements selected from group 12 of the periodic table (the first Elements) 2 types, and a ternary group II-VI compound semiconductor selected from 1 type of elements from Group 16 of the periodic table (the second element), may contain elements selected from Group 12 of the periodic table (the first element) 2 species, and a quaternary system II-VI compound semiconductor selected from two species of Group 16 elements (second elements) of the periodic table.

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

(Microparticles of crystals of group II-V compound semiconductors)

Group II-V compound semiconductors contain Group 12 elements and Group 15 elements of the periodic table.

Binary system II-V group compound semiconductors containing elements selected from group 12 of the periodic table (first element) and elements selected from group 15 of the periodic table (second element) include, for example, Zn ₃ P ₂ , Zn ₃ As ₂ , Cd ₃ P ₂ , Cd ₃ As ₂ , Cd ₃ N ₂ , or Zn ₃ N ₂ .

A group II-V compound semiconductor containing an element selected from Group 12 of the periodic table (the first element) and an element selected from Group 15 of the periodic table (the second element) may contain an element selected from Group 12 of the periodic table (1st element) 1 type, and 2 types selected from group 15 elements of the periodic table (second element) ternary system II-group V compound semiconductor, may contain elements selected from group 12 of the periodic table (the first element) 2 types, and 1 type of ternary system II-V group compound semiconductor selected from group 15 elements (second element) of the periodic table, may contain elements selected from group 12 of the periodic table (the first element) 2 type, and a quaternary system II-V group compound semiconductor selected from two types of group 15 elements (second elements) in the periodic table.

The group II-V compound semiconductor system may contain elements other than group 12 and group 15 of the periodic table as doping elements.

(Crystal fine particle of group III-V compound semiconductor)

Group III-V compound semiconductors contain elements selected from group 13 of the periodic table and elements selected from group 15. Binary system III-V compound semiconductors containing elements selected from Group 13 (first element) of the periodic table and elements selected from Group 15 (second element) of the periodic table include, for example, BP, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs, InSb, AlN, or BN.

Group III-V compound semiconductors containing elements selected from Group 13 of the Periodic Table (the first element) and elements selected from Group 15 of the Periodic Table (the second element) may contain elements selected from Group 13 of the Periodic Table (1st element) 1 type, and 2 types of ternary group III-V compound semiconductors selected from group 15 elements (second element) of the periodic table, may contain elements selected from group 13 of the periodic table (the first Elements) 2 types, and ternary group III-V compound semiconductors selected from 1 type of elements from Group 15 of the periodic table (the 2nd element), may contain elements selected from Group 13 of the periodic table (the 1st element) 2 type, and a quaternary group III-V group compound semiconductor selected from two types of group 15 elements (second elements) in the periodic table.

The group III-V compound semiconductor system may contain elements other than group 13 and group 15 of the periodic table as doping elements.

(Crystal fine particle of group III-IV compound semiconductor)

Group III-IV compound semiconductors contain elements selected from Group 13 of the periodic table and elements selected from Group 14. Binary group III-IV compound semiconductors containing elements selected from group 13 (first element) of the periodic table and elements selected from group 14 of the periodic table (second element) include, for example, B ₄ C ₃ , Al ₄ C ₃ , Ga ₄ C ₃ .

Group III-IV compound semiconductors containing elements selected from Group 13 of the Periodic Table (the first element) and elements selected from Group 14 of the Periodic Table (the second element) may contain elements selected from Group 13 of the Periodic Table (1st element) 1 type, and 2 types of ternary group III-IV compound semiconductors selected from group 14 elements (second element) of the periodic table, may contain elements selected from group 13 of the periodic table (the first element) 2 types, and 1 type of ternary group III-IV compound semiconductor selected from group 14 elements of the periodic table (the second element), may contain elements selected from the group 13 of the periodic table (the first element) 2 type, and a quaternary group III-IV group compound semiconductor selected from two types of group 14 elements (second elements) in the periodic table.

Group III-IV compound semiconductors may contain elements other than Group 13 and Group 14 of the periodic table as doping elements.

(Crystalline Microparticles of Group III-VI Compound Semiconductors)

The group III-VI compound semiconductors contain elements selected from group 13 of the periodic table and elements selected from group 16.

Binary group III-VI compound semiconductors containing elements selected from group 13 (first element) of the periodic table and elements selected from group 16 (second element) of the periodic table, such as 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.

Group III-VI compound semiconductors containing elements selected from Group 13 of the Periodic Table (the first element) and elements selected from Group 16 of the Periodic Table (the second element) may contain elements selected from Group 13 of the Periodic Table (1st element) 1 type, and 2 types of ternary group III-VI compound semiconductors selected from group 16 elements (second element) of the periodic table, may contain elements selected from group 13 of the periodic table (the first element) 2 types, and 1 type of ternary group III-VI compound semiconductors selected from group 16 elements of the periodic table (the second element), may contain elements selected from the group 13 of the periodic table (the first element) 2 type, and a quaternary group III-VI compound semiconductor selected from two types of group 16 elements (second elements) in the periodic table.

The group III-VI compound semiconductor system may contain elements other than group 13 and group 16 of the periodic table as doping elements.

(Crystalline Microparticles of Group IV-VI Compound Semiconductors)

Group IV-VI compound semiconductors contain elements selected from Group 14 of the periodic table and elements selected from Group 16. Binary group IV-VI compound semiconductors containing elements selected from group 14 of the periodic table (the first element) and elements selected from the group 16 of the periodic table (the second element), such as PbS, PbSe, and PbTe. , SnS, SnSe, or SnTe.

A group IV-VI compound semiconductor containing an element selected from Group 14 of the Periodic Table (the first element) and an element selected from Group 16 of the Periodic Table (the second element) may contain an element selected from Group 14 of the Periodic Table (1st element) 1 type, and 2 types selected from group 16 elements of the periodic table (the second element) ternary system group IV-group VI compound semiconductor, may contain elements selected from group 14 of the periodic table (the first Elements) 2 types, and a ternary group IV-VI compound semiconductor selected from 1 type of elements from Group 16 of the periodic table (the 2nd element), may contain elements selected from Group 14 of the periodic table (the 1st element) 2 type, and a quaternary system group IV-group VI compound semiconductor selected from two types of group 16 elements (second elements) in the periodic table.

Group IV-VI compound semiconductors may contain elements other than Group 14 and Group 16 of the periodic table as doping elements.

(Crystalline fine particles of transition metal-p-block compound semiconductor)

The transition metal-p-block compound semiconductor contains an element selected from transition metal elements and an element selected from p-block elements.

A binary transition metal-p-block compound semiconductor containing an element (first element) selected from transition metal elements of the periodic table and an element (second element) selected from p-block elements of the periodic table, For example, NiS and CrS are mentioned.

A transition metal-p-block compound semiconductor containing an element selected from the transition metal elements of the periodic table (the first element) and an element selected from the p-block element of the periodic table (the second element) may contain A ternary system transition metal-p-block compound semiconductor selected from one type of element (first element) of transition metal elements in the periodic table and two types of element selected from p-block element (second element) can be It is a ternary transition metal-p-block containing two kinds of elements (first element) selected from the transition metal elements of the periodic table, and one kind of element (second element) selected from the p-block elements of the periodic table The segment compound semiconductor may be a quaternary transition system containing two types of elements (first element) selected from the transition metal elements of the periodic table and two types of elements (second element) selected from the p-block element of the periodic table Metal-p-block compound semiconductors.

The transition metal-p-block compound semiconductor system may contain transition metal elements of the periodic table and elements other than the p-block element as doping elements.

Specific examples of the above-mentioned ternary and quaternary semiconductors include ZnCdS, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, ZnCdSSe, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, HgZnSTe, GaNP, GaNAs, GaPAs, AlNP, AlNAs, AlPAs, InNP, InNAs, InPAs, GaAlNP, GaAlNAs, GaAlPAs, GaInNP, GaInNAs, GaInPAs, InAlNP, InAlNAs, CuInS ₂ , or InAlPAs, or the like.

(perovskite compound)

As an example of the semiconductor fine particles, fine particles of a perovskite compound can be mentioned, for example.

The perovskite compound is a compound having a perovskite crystal structure containing A, B, and X as constituents.

In the present invention, A is a component located at each vertex of a hexahedron with B as the center in the aforementioned perovskite crystal structure, and is a monovalent cation.

X represents a component located at each vertex of an octahedron centered on B in the aforementioned 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 in the center of the hexahedron having A at the vertex and the octahedron having X at the vertex in the aforementioned perovskite crystal structure, and is a metal ion.

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

In a three-dimensional structure, the composition formula of the perovskite compound is represented by ABX _(3+δ) .

In a two-dimensional structure, the composition formula of the perovskite compound is represented by A ₂ BX _(4+δ) .

Here, the aforementioned δ is a number that can be appropriately changed in accordance with the charge balance of B, and is -0.7 or more and 0.7 or less.

For example, when A is a monovalent cation, B is a divalent cation, and X is a monovalent anion, δ can be selected so that the aforementioned compound is neutral (charge 0).

In the above-mentioned three-dimensional structure, there is a three-dimensional network of octahedrons whose vertices are represented by _{BX 6 with B as the center and whose vertices are X.}

In the above-mentioned two-dimensional structure, by sharing the four vertices X of the same plane with the eight planes represented by _{BX 6 with B as the center and the vertex as X, a layer composed of BX 6} that is connected in two dimensions is formed. and a structure composed of layers composed of A, which are stacked alternately.

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

In the case of the compound having a perovskite crystal structure with a three-dimensional structure, a peak derived from (hkl)=(001) can usually be confirmed at the position of 2θ=12 to 18° in the X-ray diffraction pattern. , or a peak derived from (hkl)=(100) was confirmed at the position of 2θ=18 to 25°. More preferably, the peak derived from (hkl)=(001) can be confirmed at the position of 2θ=13 to 16°, or the peak derived from (hkl)=(100) can be confirmed at the position of 2θ=20 to 23°. peak.

In the case of the compound having the aforementioned perovskite crystal structure having a two-dimensional structure, in the X-ray diffraction pattern, a peak derived from (hkl)=(002) can usually be confirmed at the position of 2θ=1 to 10°, It can be confirmed that the peak derived from (hkl)=(002) is better at the position of 2θ=2 to 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 the general formula (1), A is a monovalent cation, B is a metal ion, and X is one or more anions selected from the group consisting of a halide ion and a thiocyanate ion. ]

[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 aforementioned perovskite crystal structure, and is a monovalent cation. As a monovalent cation system, a cesium ion, an organic ammonium ion, or an amidine ion is mentioned, for example. In the perovskite compound, when A is a cesium ion, an organic ammonium ion with 3 or less carbon atoms, or an amidine ion with 3 or less carbon atoms, in general, the perovskite compound has ABX _(3+δ) The 3-dimensional structure shown.

Among the compounds, series A is preferably cesium ion or organic ammonium ion.

Specifically, the organic ammonium ion of A is a cation represented by the following general formula (A3).

In the general formula (A3), R ⁶ to R ⁹ each independently represent a hydrogen atom, an alkyl group which may have an amino group as a substituent, or a cycloalkyl group which may have an amino group as a substituent. 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, or may have an amine 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, more preferably 1 to 3.

The cycloalkyl system represented by R ⁶ to R ⁹ may have an alkyl group as a substituent or an amine 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, more preferably 3 to 8. The carbon number system also includes the carbon number of the substituent.

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

By reducing the number of alkyl and cycloalkyl groups that the general formula (A3) can contain, and reducing the number of carbon atoms in the alkyl and cycloalkyl groups, a perovskite crystal structure with a 3-dimensional structure with high luminous intensity can be obtained the compound.

When the number of carbon atoms in the alkyl group or the cycloalkyl group is 4 or more, a compound having a 2-dimensional and/or quasi-2D perovskite-type crystal structure in a part or the whole can be obtained. When the 2-dimensional perovskite-type crystal structure is infinitely stacked, it becomes the same as the 3-dimensional perovskite-type crystal structure (reference: PP Boix et al., J.Phys.Chem.Lett.2015,6,898-907 Wait).

The total number of carbon atoms contained in the alkyl group represented by R ⁶ to R ⁹ and the cycloalkyl group is preferably 1 to 4, and one of R ⁶ to R ⁹ has 1 to 3 carbon atoms. More preferably, an alkyl group and 3 of R ⁶ to R ⁹ are hydrogen atoms.

The alkyl group of R ⁶ to R ⁹ can be exemplified by methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary-butyl, tertiary-butyl, n-pentyl, isopentyl base, neopentyl, tertiary-pentyl, 1-methylbutyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, 2,2-dimethylbutyl, 2,3- Dimethylbutyl, n-heptyl, 2-methylhexyl, 3-methylhexyl, 2,2-dimethylpentyl, 2,3-dimethylpentyl, 2,4-dimethylpentyl , 3,3-dimethylpentyl, 3-ethylpentyl, 2,2,3-trimethylbutyl, n-octyl, isooctyl, 2-ethylhexyl, nonyl, decyl , undecyl, dodecyl, thirteen, fourteen, fifteen, sixteen, seventeen, eighteen, nineteen, twenty .

Cycloalkyl R ⁶ to R ⁹ may be for example the number of such R ⁶ to R ⁹ are illustrated an alkyl group of the alkyl group having 3 or more carbon atoms form a ring, its one case can be exemplified cyclopropyl, cyclobutyl, cyclopentyl , cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, norbornyl, isobornyl, 1-adamantyl, 2-adamantyl, tricyclodecyl, etc.

The organic ammonium ions shown in A are represented by CH ₃ NH ₃ ⁺ (also known as methyl ammonium ion), C ₂ H ₅ NH ₃ ⁺ (also known as ethyl ammonium ion) or C ₃ H ₇ NH ₃ ⁺ (also known as ethyl ammonium ion) It is called propylammonium ion) is better, CH ₃ NH ₃ ⁺ or C ₂ H ₅ NH ₃ ⁺ is better, CH ₃ NH ₃ ⁺ is the best.

The amidine ion represented by A includes, for example, the amidine ion represented by the following general formula (A4).

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

In the 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 cycloalkyl group which may have an amino group as a substituent.

The alkyl group represented by R ¹⁰ to R ¹³ may be linear or branched, and may have an amine group as a substituent.

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

The cycloalkyl group represented by R ¹⁰ to R ¹³ may have an alkyl group as a substituent or an amine 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, more preferably 3 to 8. The number of carbon atoms refers to the number of carbon atoms containing a substituent.

Specific examples of the alkyl groups of R ¹⁰ to R ^{13 include the alkyl groups exemplified for R 6} to R ⁹ .

Specific examples of the cycloalkyl group of R ¹⁰ to R ¹³ include, for example, the cycloalkyl groups exemplified for R ⁶ to R ⁹ .

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

By reducing the number of alkyl groups and cycloalkyl groups and reducing the number of carbon atoms in the alkyl groups and cycloalkyl groups contained in the general formula (A4), a perovskite compound having a 3-dimensional structure with high luminescence intensity can be obtained.

When the number of carbon atoms in the alkyl group or cycloalkyl group is 4 or more, a compound having a part or all of a 2D and/or quasi-2D perovskite crystal structure can be obtained. In addition, the total number of carbon atoms contained in the alkyl group represented by ^{R 10} to R ^{13 and the cycloalkyl group is preferably 1 to 4, and R 10} is an alkyl group with 1 to 3 carbon atoms and R ^More preferably, 11 to R ¹³ are hydrogen atoms.

[B]

In the perovskite compound, B is a component located in the center of the hexahedron having A at the vertex and the octahedron having X at the vertex in the perovskite crystal structure, and represents a metal ion. The metal ion of the B component may contain one or more kinds of ions selected from the group consisting of a monovalent metal ion, a divalent metal ion, and a trivalent metal ion. The B series 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 series 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, but X may contain bromide ions, for example.

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

As a perovskite compound having a _{3-dimensional structure represented by ABX (3+δ)} and having a perovskite-type crystal structure, specific examples thereof include CH ₃ NH ₃ PbBr ₃ , CH ₃ NH ₃ PbCl ₃ , CH ₃ NH ₃ PbI ₃ , CH ₃ NH ₃ PbBr _(3-y) I _y (0<y<3), CH ₃ NH ₃ PbBr _(3-y) Cl _y (0<y<3 ), (H ₂ N=CH-NH ₂ )PbBr ₃ , (H ₂ N=CH-NH ₂ )PbCl ₃ , (H ₂ N=CH-NH ₂ )PbI ₃ , 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 ₂ )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) C y} (0<y<3), CH ₃ NH ₃ PbBr _{(3-y) C 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 ₃ 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) C y} (0<a≦0.7, 0≦δ≦0.7, 0<y<3) etc. are preferred.

As a perovskite compound, a compound having a perovskite-type crystal structure having a two-dimensional structure represented by _{A 2} BX _{(4+δ) , specific examples thereof 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 Br _(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) C _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 Br _(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) C 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) C 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) C y} (0<a≦0.7, 0≦δ≦0.7, 0<y<4) etc. are preferred.

≪Luminescence spectrum≫

The perovskite compound is a light-emitting body that can emit 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 A wavelength range of 600 nm or less, more preferably 580 nm or less, can emit fluorescence having a maximum intensity peak.

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

Another aspect of the present invention is that when X in the perovskite compound is a bromide ion, the fluorescence peak is usually 480-700 nm, preferably 500-600 nm, more preferably 520-580 nm.

When X is an iodide ion, it is usually 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. The maximum peak fluorescence.

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

Another aspect of the present invention is that when X in the perovskite compound is an iodide ion, the fluorescence peak is usually 520 to 800 nm, preferably 530 to 750 nm, more preferably 540 to 730 nm.

When X is a chloride ion, it is usually 300 nm or more, 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. The fluorescence of the maximum intensity peak.

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

Another aspect of the present invention is that when X in the perovskite compound is a chloride ion, the fluorescence peak is usually 300-600 nm, preferably 310-580 nm, more preferably 330-550 nm.

(2) Organic compounds having a hydrogen thiol group

The organic compound having a sulfhydryl group may be an organic compound having one or a plurality of sulfhydryl groups.

The organic compound having a thiol group may also be a compound having a thiol group represented by the following general formula (A5).

R ¹⁴ -SH. . . (A5)

In the general formula (A5), R ¹⁴ represents a monovalent organic group. Examples of the organic group include groups such as an optionally substituted alkyl group or an optionally substituted cycloalkyl group.

When R ¹⁴ is an alkyl group, it may be linear or branched; it may have a thiol group or an alkoxysilyl group as a substituent. The number of carbon atoms of the alkyl group is usually 1 to 20, preferably 5 to 20, more preferably 8 to 20. The aforementioned number of carbon atoms includes the number of carbon atoms of the substituent.

When R ¹⁴ is a cycloalkyl group, it may have a hydrogen thio group, an alkoxysilyl group, or an alkyl group as a substituent. The number of carbon atoms of the cycloalkyl group is usually 3 to 30, preferably 3 to 20, more preferably 3 to 11. The aforementioned number of carbon atoms refers to the number of carbon atoms containing a substituent.

Among these, R ¹⁴ is preferably an alkyl group.

Specific examples of the alkyl group for R ^{14 include the alkyl groups exemplified for R 6} to R ⁹ .

Specific examples of the cycloalkyl group for R ^{14 include the cycloalkyl groups exemplified for R 6} to R ⁹ .

In the compound having a thiol group represented by the above general formula (A5), when R ¹⁴ is an alkyl group having an alkoxysilyl group as a substituent, the above general formula (A5) includes the following general formula (A5-1) .

In the general formula (A5-1), R ^14a represents an alkylene group, R ^14b represents an alkyl group, and R ^14c to R ^14d each independently represent a hydrogen atom, an alkyl group, or an alkoxy group.

Specific examples of the alkylene group of R ^14a include groups obtained by removing one hydrogen atom from one of the alkyl groups ^{exemplified by R 6} to R ^{9 .}

Specific examples of the alkyl groups of R ^14b to R ^{14d include the alkyl groups exemplified by R 6} to R ⁹ .

The alkoxy group of R ^14c to R ^14d can be exemplified by the monovalent group in which the linear or branched alkyl group exemplified by R ⁶ to R ^{9 is bonded to an oxygen atom.}

R ^14c to R ^{14d are} preferably alkoxy groups.

In the general formula (A5), SH represents a thiol group.

A part or all of the organic compound having a hydrogen thio group represented by the general formula (A5) can be adsorbed on the surface of the semiconductor fine particles of the present invention, and can also be dispersed in the composition.

The organic compound having a hydrogen thiol group represented by the general formula (A5) is preferably 1-dodecanethiol, 1-eicosanethiol, 1-octadecanethiol, 1-pentadecanethiol, 1-tetradecanethiol, 1-hexadecanethiol, 1-decanethiol, 1-docosanethiol, 1,10-decanedithiol, (3-hydrothiopropyl) ) trimethoxysilane; more preferably 1-hexadecanethiol, 1-decanethiol, 1-docosanethiol, 1,10-decanedithiol, (3-hydrothiopropane) base) trimethoxysilane.

The organic compound of (2) is preferably selected from the group consisting of a compound having a thiosulfur group represented by the aforementioned general formula (A5) and a compound having a sulfhydryl group represented by the aforementioned general formula (A5-1). at least one of them.

In another aspect of the present invention, (2) an organic compound having a thiol group, an organic compound _{having an ionic group other than a group represented by -NH 3} ⁺ and a group represented by -COO ^- , and a halogenated hydrocarbon may be used. Compounds, or organic compounds having an amine group, an alkoxy group, and a silicon atom.

(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, the solubility of the semiconductor fine particles to the polymerizable compound is preferably low.

The term "polymerizable compound" in this specification means a compound of a monomer having a polymerizable group.

For example, when producing at room temperature and normal pressure, the aforementioned polymerizable compound is not particularly limited, and examples thereof include known polymerizable compounds such as styrene and methyl methacrylate. Among them, the polymerizable compound is preferably one or both of acrylates and methacrylates which are the monomer components of the acrylic resin.

The polymer contained in the composition according to the present invention is not particularly limited, but at the temperature for producing the composition, the solubility of the semiconductor fine particles to the polymer is preferably low.

For example, when produced at room temperature and normal pressure, the aforementioned polymer system is not particularly limited, and examples thereof include known polymers such as polystyrene and methacrylic resin. Among them, the polymer system is preferably an acrylic resin. Acrylic resins contain structural units derived from either or both of acrylates and methacrylates.

Among the structural units of the polymerizable compound and polymer of (3), when the acrylate and/or methacrylate and the structural units derived from them are expressed in mol%, they are 10% or more with respect to all the structural units, and can be 30% or more, 50% or more, 80% or more, or 100%.

(4) At least one selected from the group consisting of ammonia, amines, carboxylic acids, and salts or ions of these

The composition according to the present invention can take the form of ammonia, amine, and carboxylic acid, and the aforementioned compounds, and can contain at least one selected from the group consisting of salts and ions thereof.

That is, the composition according to the present invention may contain a group selected from the group consisting of ammonia, amine, carboxylic acid, ammonia salt, amine salt, carboxylic acid salt, ammonia ion, amine ion, and carboxylic acid ion At least 1 of the group.

Ammonia, amines, and carboxylic acids, as well as salts or ions of these, often function as capping ligands. The so-called capping ligand is a compound which is adsorbed on the surface of the semiconductor compound and has the function of stabilizing and dispersing the semiconductor compound in the composition. Examples of ions or salts (ammonium salts, etc.) of ammonia or amines include ammonium cations represented by the general formula (A1) described later, and ammonium salts containing them. As an ion or salt (carboxylate etc.) of a carboxylic acid, the carboxylate anion represented by general formula (A2) mentioned later, and the carboxylate containing it are mentioned, for example. The composition system according to the present invention may contain either an ammonium salt or the like, a carboxylate or the like, or may contain both.

As an ammonium salt, the ammonium salt containing the ammonium cation represented by general formula (A1) is mentioned, for example.

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

The alkyl groups 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, more preferably 8 to 20.

The cycloalkyl system represented by R ¹ to R ⁴ may have an alkyl group as a substituent. The number of carbon atoms of the cycloalkyl group is usually 3 to 30, preferably 3 to 20, more preferably 3 to 11. The number of carbon atoms refers to the number of carbon atoms containing a substituent.

The ^{unsaturated hydrocarbon groups of R 1} to R ⁴ may be linear or branched.

The ^{number of carbon atoms of the unsaturated hydrocarbon groups of R 1} to R ⁴ is usually 2 to 20, preferably 5 to 20, more preferably 8 to 20.

R ¹ to R ⁴ are preferably hydrogen atoms, alkyl groups, or unsaturated hydrocarbon groups. The unsaturated hydrocarbon group is preferably an alkenyl group. 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 preferably hydrogen atoms.

Specific examples of the alkyl groups of R ¹ to R ^{4 include the alkyl groups exemplified for R 6} to R ⁹ .

Specific examples of the cycloalkyl groups of R ¹ to R ^{4 include the cycloalkyl groups exemplified for R 6} to R ⁹ .

The alkenyl groups of R ¹ to R ^{4 are among the aforementioned linear or branched alkyl groups exemplified in R 6} to R ⁹ , and the single bond (CC) between carbon atoms, which can be exemplified, is substituted with a double bond Bond (C=C), the position of the double bond is not limited.

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

The relative anion system is not particularly limited, but for example, halide ions and carboxylate ions of ^{Br -} , Cl ^- , I ^- , and F ^{- can be mentioned as preferable examples.}

Preferred examples of the ammonium salts having the ammonium cation represented by the general formula (A1) and the counter anion include n-octylammonium salt and oleylammonium salt.

As a carboxylate type|system|group, the carboxylate containing the carboxylate anion represented by following general formula (A2) is mentioned, for example.

R ⁵ -CO ₂ ^- ‧‧‧(A2)

In the general formula (A2), R ⁵ represents a monovalent organic group. The organic group is preferably a hydrocarbon group, and among them, for example, an alkyl group, a cycloalkyl group, and an unsaturated hydrocarbon group are preferably mentioned.

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, more preferably 8 to 20.

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

The ^{unsaturated hydrocarbon group of R 5} may be linear or branched.

The ^{number of carbon atoms of the unsaturated hydrocarbon group of R 5} is usually 2 to 20, preferably 5 to 20, more preferably 8 to 20.

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

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

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

Specific examples of the alkenyl group 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 oleic acid anion. The relative cation system of the carboxylate anion represented by the general formula (A2) is not particularly limited, but for example, protons, alkali metal cations, alkaline earth metal cations, ammonium cations and the like can be mentioned as preferred examples.

(Other) Solvents

The solvent which may be contained in the composition of the present invention is a medium for dispersing the semiconductor fine particles, and examples thereof include those which are difficult to dissolve the semiconductor fine particles.

In this specification, the term "solvent" refers to a substance obtained in a liquid state at 1 atmospheric pressure and 25°C (however, polymerizable compounds and polymers are excluded).

烷、1,3-二氧雜環戊烷、4-甲基二氧雜環戊烷、四氫呋喃、甲基四氫呋喃、苯甲醚、苯乙醚等醚；甲醇、乙醇、1-丙醇、2-丙醇、1-丁醇、2-丁醇、三級-丁醇、1-戊醇、2-甲基-2-丁醇、甲氧基丙醇、二丙酮醇、環己醇、2-氟乙醇、2,2,2-三氟乙醇、2,2,3,3-四氟-1-丙醇等醇；乙二醇單甲基醚、乙二醇單乙基醚、乙二醇單丁基醚、乙二醇單乙基醚乙酸酯、三乙二醇二甲基醚等二醇醚；N-甲基-2-吡咯啶酮、N,N-二甲基甲醯胺、乙醯胺、N,N-二甲基乙醯胺等具有醯胺基之有機溶劑；乙腈、異丁腈、丙腈、甲氧基乙腈等具有腈基之有機溶劑；碳酸伸乙酯、碳酸伸丙酯等具有烴基之有機溶劑；二氯甲烷、氯仿等具有經鹵素化的烴基之有機溶劑；正戊烷、環己烷、正己烷、苯、甲苯、二甲苯等具有烴基之有機溶劑；二甲基亞碸等。 Examples of the solvent system include esters such as methyl formate, ethyl formate, propyl formate, amyl formate, methyl acetate, ethyl acetate, and amyl acetate; γ-butyrolactone, acetone, dimethyl ketone, diiso Butyl ketone, cyclopentanone, cyclohexanone, methylcyclohexanone and other ketones; diethyl ether, methyl-tertiary-butyl ether, diisopropyl ether, dimethoxymethane, dimethoxy Ethane, 1,4-di

alkane, 1,3-dioxolane, 4-methyldioxolane, tetrahydrofuran, methyltetrahydrofuran, anisole, phenethyl ether and other ethers; methanol, ethanol, 1-propanol, 2- Propanol, 1-butanol, 2-butanol, tertiary-butanol, 1-pentanol, 2-methyl-2-butanol, methoxypropanol, diacetone alcohol, cyclohexanol, 2- Alcohols such as fluoroethanol, 2,2,2-trifluoroethanol, 2,2,3,3-tetrafluoro-1-propanol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol Monobutyl ether, ethylene glycol monoethyl ether acetate, triethylene glycol dimethyl ether and other glycol ethers; N-methyl-2-pyrrolidone, N,N-dimethylformamide , acetamide, N,N-dimethylacetamide and other organic solvents with amide groups; acetonitrile, isobutyronitrile, propionitrile, methoxyacetonitrile and other organic solvents with nitrile groups; ethyl carbonate, Organic solvents with hydrocarbon groups such as propylene carbonate; organic solvents with halogenated hydrocarbon groups such as dichloromethane and chloroform; organic solvents with hydrocarbon groups such as n-pentane, cyclohexane, n-hexane, benzene, toluene and xylene ; Dimethyl methylene and so on.

烷、1,3-二氧雜環戊烷、4-甲基二氧雜環戊烷、四氫呋喃、甲基四氫呋喃、苯甲醚、苯乙醚等醚、乙腈、異丁腈、丙腈、甲氧基乙腈等具有腈基的有機溶劑；碳酸伸乙酯、碳酸伸丙酯等具有碳酸酯基之有機溶劑；二氯甲烷、氯仿等具有經鹵素化的烴基之有機溶劑；正戊烷、環己烷、正己烷、苯、甲 苯、二甲苯等具有烴基的有機溶劑係極性低，咸認為難以溶解半導體微粒子，故較佳，二氯甲烷、氯仿等具有經鹵素化的烴基之有機溶劑；正戊烷、環己烷、正己烷、苯、甲苯、二甲苯等烴系有機溶劑為更佳。 Among these, methyl formate, ethyl formate, propyl formate, amyl formate, methyl acetate, ethyl acetate, amyl acetate and other esters; γ-butyrolactone, acetone, dimethyl ketone, diiso Butyl ketone, cyclopentanone, cyclohexanone, methylcyclohexanone and other ketones; diethyl ether, methyl-tertiary-butyl ether, diisopropyl ether, dimethoxymethane, dimethoxy Ethane, 1,4-di

Alkane, 1,3-dioxolane, 4-methyldioxolane, tetrahydrofuran, methyltetrahydrofuran, anisole, phenethyl ether and other ethers, acetonitrile, isobutyronitrile, propionitrile, methoxy Organic solvents with nitrile groups such as acetonitrile; organic solvents with carbonate groups such as ethylidene carbonate and propylidene carbonate; organic solvents with halogenated hydrocarbon groups such as dichloromethane and chloroform; n-pentane, cyclohexane Organic solvents with hydrocarbon groups such as alkane, n-hexane, benzene, toluene, and xylene are low in polarity and are considered difficult to dissolve semiconductor fine particles, so organic solvents with halogenated hydrocarbon groups such as dichloromethane and chloroform are preferred; n-pentane Hydrocarbon-based organic solvents such as alkane, cyclohexane, n-hexane, benzene, toluene, and xylene are more preferable.

<Regarding the blending ratio of each ingredient>

The composition of this embodiment contains (1), (2) and (3).

(1) Semiconductor fine particles

(2) Organic compounds with hydrogen sulfhydryl groups

(3) At least one selected from the group consisting of a polymerizable compound and a polymer

The composition of the present embodiment contains (1), (2), and (3'), or the total content of (1), (2), and (3') relative to the total mass of the composition may be 90% by mass or more of the composition.

(1) Semiconductor fine particles

(2) Organic compounds with hydrogen sulfhydryl groups

(3') polymer

In the composition of the present embodiment, the blending ratio of (1) and (2) is sufficient as long as the effect of improving the quantum yield by the organic compound of (2) can be exerted, and the ratios of (1) and (2) can be used. type, etc. are appropriately determined.

In the composition of the present embodiment, when (1) the semiconductor fine particles are fine particles of a perovskite compound, the molar ratio of the metal ion of B of the perovskite compound and the organic compound of (2) [(2)/B] It can be 0.001 to 1000, 0.01 to 700, or 0.1 to 500.

In the composition of the present embodiment, when (1) the semiconductor fine particles are fine particles of a perovskite compound, and the organic compound (2) is a compound having a hydrogen sulfide group represented by the general formula (A5), the perovskite compound The molar ratio [(A5)/B] of the metal ion of B and the organic compound of (A5) is 1 to 500, may be 30 to 300, or may be 100 to 200.

(1) The range related to the blending ratio of (2) is the composition within the above-mentioned range, and the effect of improving the quantum yield of the organic compound of (2) is preferable because it can be particularly well exhibited.

In one aspect of the present invention, when (1) the semiconductor fine particles are fine particles of a perovskite compound, and the organic compound of (2) is 1-hexadecanethiol, the metal ion of B of the perovskite compound and the metal ion of (2) The molar ratio [(2)/B] of the organic compound is preferably 1 to 300, more preferably 5 to 250, still more preferably 30 to 200, and particularly preferably 60 to 180.

In another aspect of the present invention, when (1) the semiconductor fine particles are fine particles of a perovskite compound, and the organic compound of (2) is 1-decanethiol, the metal ion of B of the perovskite compound and the metal ion of (2) The molar ratio [(2)/B] of the organic compound is preferably 10 to 300, more preferably 25 to 200, still more preferably 80 to 180.

In yet another aspect of the present invention, when (1) the semiconductor fine particles are fine particles of a perovskite compound, and the organic compound of (2) is 1-docosanethiol, the metal ion of B of the perovskite compound is mixed with (2) ), the molar ratio [(2)/B] of the organic compound is preferably 5 to 100, more preferably 20 to 60.

In another aspect of the present invention, when (1) the semiconductor fine particles are fine particles of a perovskite compound, and the organic compound of (2) is 1,10-decanethiol, the metal ion of B of the perovskite compound and (2) ), the molar ratio [(2)/B] of the organic compound is preferably 1 to 200, more preferably 10 to 120, still more preferably 30 to 100.

Another aspect of the present invention is that when (1) the semiconductor fine particles are fine particles of a perovskite compound, and the organic compound (2) is (3-hydrothiopropyl)trimethoxysilane, B of the perovskite compound The molar ratio [(2)/B] of the metal ion to the organic compound of (2) is preferably 5 to 200, more preferably 40 to 120.

In the composition of the present embodiment containing (1), (2) and (3), the blending ratio of (1) and (3) is as long as the light-emitting effect produced by the semiconductor fine particles of (1) can be well exhibited. The degree is sufficient, and can be appropriately determined according to the types of (1) to (3).

In the composition of the present embodiment, the mass ratio [(1)/(3)] of (1) and (3) is 0.00001 to 10, and may be 0.0001 to 1 or 0.0005 to 0.1.

The ranges related to the blending ratios of (1) and (3) are compositions within the above-mentioned ranges, which are less likely to cause aggregation of the semiconductor fine particles of (1), and are preferable in terms of exhibiting good luminescence properties.

In the composition of the present embodiment containing (1), (2), and (3'), the mixing ratio of (1) and (3') is as long as the light emission generated by the semiconductor fine particles of (1) The degree to which the effect is well exerted is sufficient, and can be appropriately determined according to the types of (1) and (3').

In the composition of the present embodiment, the mass ratio [(1)/(3')] of (1) and (3') is 0.00001 to 10, may be 0.0001 to 1, or 0.0005 to 0.1.

(1) The range related to the blending ratio of (3') is a composition within the above-mentioned range, which is preferable in that the luminescence property is well exhibited.

<Production method of composition>

Hereinafter, the method for producing the composition of the present invention will be described with reference to an embodiment. According to the method for producing the composition of the present embodiment, the composition of the embodiment of the present invention can be produced. In addition, the composition of this invention is not limited to what was manufactured according to the manufacturing method of the composition of the following embodiment.

<(1) Manufacturing method of semiconductor fine particles>

(crystalline fine particles of group II-VI compound semiconductors, crystalline fine particles of group II-V compound semiconductors, crystalline fine particles of group III-V compound semiconductors, crystalline fine particles of group III-IV compound semiconductors, crystalline fine particles of group III-VI compound semiconductors, Method for producing compound semiconductor crystalline fine particles, group IV-VI compound semiconductor crystalline fine particles, and transition metal-p-block compound semiconductor crystalline fine particles)

The method for producing semiconductor fine particles includes, for example, a method of heating a liquid mixture obtained by mixing a monomer or compound of an element constituting semiconductor fine particles and a fat-soluble solvent.

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

The fat-soluble solvent includes, for example, a nitrogen-containing compound having a hydrocarbon group having 4 to 20 carbon atoms, an oxygen-containing compound having a hydrocarbon group having 4 to 20 carbon atoms, and the like. Examples of hydrocarbon groups having 4 to 20 carbon atoms include saturated aliphatic hydrocarbon groups such as n-butyl, isobutyl, n-pentyl, octyl, decyl, dodecyl, hexadecyl, and octadecyl; oil unsaturated aliphatic hydrocarbon groups such as cyclopentyl groups; alicyclic hydrocarbon groups such as cyclopentyl and cyclohexyl groups; aromatic hydrocarbon groups such as phenyl, benzyl, naphthyl, and naphthyl methyl groups, etc., among which, saturated aliphatic hydrocarbon groups or unsaturated aliphatic groups Hydrocarbon groups are preferred. Examples of nitrogen-containing compounds include amines and amides, and examples of oxygen-containing compounds include fatty acids. Among such fat-soluble solvents, nitrogen-containing compounds with hydrocarbon groups having 4 to 20 carbon atoms are preferred, such as n-butylamine, isobutylamine, n-amylamine, n-hexylamine, octylamine, decylamine Alkyl amines such as base amine, dodecyl amine, hexadecyl amine, octadecyl amine, etc., and alkenyl amines such as oleyl amine are preferred. Such a liposoluble solvent can be bonded to the particle surface, and the bonding mode can be chemical bonding such as covalent bonding, ionic bonding, coordinate bonding, hydrogen bonding, and van der Waals bonding.

The heating temperature of the mixed solution can be appropriately set according to the types of monomers and compounds used. For example, it is preferably set in the range of 130 to 300°C, and more preferably in the range of 240 to 300°C. When the heating temperature is equal to or higher than the above lower limit value, the crystal structure is likely to be simplified, which is preferable. In addition, the heating time can also be appropriately set according to the type of the monomer or compound used and the heating temperature, but it is usually set in the range of several seconds to several hours, and more preferably in the range of 1 to 60 minutes. .

In the method for producing semiconductor fine particles of the present invention, the heated mixed solution is cooled and then separated into a supernatant liquid and a precipitate. The separated semiconductor fine particles (precipitate) can also be placed in an organic solvent (such as chloroform, toluene, hexane, n-butanol, etc.) to be a solution containing semiconductor fine particles. Or after the heated mixed solution is cooled, it is separated into a supernatant liquid and a precipitate, and an insoluble or insoluble solvent (such as methanol, ethanol, acetone, acetonitrile, etc.) can be added to the supernatant liquid after the separation. A precipitate is generated, and the precipitate is collected and placed in the organic solvent to obtain a solution containing semiconductor fine particles.

(Method for producing crystal fine particles of perovskite compound)

The semiconductor fine particles of the perovskite compound related to the present invention can be obtained by referring to known documents (Nano Lett. 2015, 15, 3692-3696, ACS Nano, 2015, 9, 4533-4542) by the following method. manufacture.

<The first embodiment of the method for producing crystal fine particles of a perovskite compound>

For example, the method for producing the semiconductor fine particles of the perovskite compound according to the present invention includes, for example, a step including a step of dissolving the components B, X, and A in a solvent to obtain a solution, and mixing the obtained solution with the semiconductor fine particles. The manufacturing method of the solvent mixing step in which the solubility of the solvent is lower than that of the solvent used in the step of obtaining a solution.

More specifically, there may be mentioned, for example, a production method comprising the following steps: dissolving the compound containing the B component and the X component, and the compound containing the A component or the A component and the X component in a solvent to obtain a solution; and dissolving the obtained The solubility of the solution and the semiconductor fine particles in the solvent is lower than that of the solvent used in the step of obtaining the solution, and the solvent is mixed.

Also, for example, a production method comprising the following steps: a step of obtaining a solution by adding a compound containing component B and component X, and a compound containing component A or component A and component X to a high-temperature solvent and dissolving it; and the step of cooling the resulting solution.

Hereinafter, the production method comprising the steps of dissolving a compound containing B component and X component, and a compound containing A component or A component and X component in a solvent to obtain a solution will be described; The solvent used in the solvent mixing step is lower in solubility than the step of obtaining the solution.

In addition, the solubility means the solubility in the temperature at which the step of mixing is performed.

The aforementioned manufacturing method preferably includes a step of adding a capping ligand from the viewpoint of stabilizing and dispersing the semiconductor fine particles. The capping ligand is preferably added before the above-mentioned mixing step, and the capping ligand can also be added to the solution after dissolving the components A, B and X, or added to the solvent of the semiconductor particles. The solvent used in the step of obtaining the solution has a lower solubility than that used in the step of obtaining the solution, and it can also be added to the solution obtained by dissolving the components A, B, and X, and the solubility of the semiconductor fine particles in the solvent is higher than the solvent used in the step of obtaining the solution. of both lower solvents.

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

The aforementioned step of mixing the solution and the semiconductor microparticles with a solvent having a lower solubility in the solvent than the solvent used in the step of obtaining the solution can be obtained by (1) dropping the solution into the semiconductor microparticles with a lower solubility in the solvent than the solvent. In this step, the solvent used is a lower solvent, or (II) the solubility of the semiconductor particles dropped into the solution in the solvent is lower than that of the solvent used in the step of obtaining the solution. From the viewpoint of improving dispersibility, (I) is preferred.

When dripping, it is preferable to perform stirring from the viewpoint of improving dispersibility.

In the step of mixing the solution and the semiconductor microparticles with a solvent having a lower solubility in the solvent than the solvent used in the step of obtaining the solution, the temperature is not particularly limited, but it is necessary to ensure that the compound having a perovskite crystal structure is easily precipitated. From the viewpoint, the range of -20 to 40°C is preferable, and the range of -5 to 30°C is more preferable.

烷、1,3-二氧雜環戊烷、4-甲基二氧雜環戊烷、四氫呋喃、甲基四氫呋喃、苯甲醚、苯乙醚等醚；乙腈、異丁腈、丙腈、甲氧基乙腈等具有腈基的有機溶劑；碳酸伸乙酯、碳酸伸丙酯等具有碳酸酯基的有機溶劑；二氯甲烷、氯仿等具有經鹵素化的烴基的有機溶劑；正戊烷、環己烷、正己烷、苯、甲苯、二甲苯等具有烴基 的有機溶劑所成群組中的2種溶劑。 The semiconductor microparticles used in the above-mentioned production method are not particularly limited in terms of two types of solvents having different solubility in the solvent, but may be selected from, for example, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2- Butanol, tertiary-butanol, 1-pentanol, 2-methyl-2-butanol, methoxypropanol, diacetone alcohol, cyclohexanol, 2-fluoroethanol, 2,2,2-tris Alcohols such as fluoroethanol, 2,2,3,3-tetrafluoro-1-propanol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol mono Ethyl ether acetate, triethylene glycol dimethyl ether and other glycol ethers; N,N-dimethylformamide, acetamide, N,N-dimethylacetamide, etc. have amide groups organic solvents; dimethyl formate, methyl formate, ethyl formate, propyl formate, amyl formate, methyl acetate, ethyl acetate, amyl acetate and other esters; γ-butyrolactone, N-methyl -2-pyrrolidone, acetone, dimethyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methylcyclohexanone and other ketones; diethyl ether, methyl-tertiary-butyl ether , diisopropyl ether, dimethoxymethane, dimethoxyethane, 1,4-dimethoxyethane

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

The solvent used in the step of obtaining the solution included in the above-mentioned production method is preferably a solvent with high solubility of the semiconductor particles in the solvent. , 1-propanol, 2-propanol, 1-butanol, 2-butanol, tertiary-butanol, 1-pentanol, 2-methyl-2-butanol, methoxypropanol, diacetone Alcohols, cyclohexanol, 2-fluoroethanol, 2,2,2-trifluoroethanol, 2,2,3,3-tetrafluoro-1-propanol and other alcohols; ethylene glycol monomethyl ether, ethylene glycol Alcohol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, triethylene glycol dimethyl ether and other glycol ethers; N,N-dimethylformamide, ethylene glycol Organic solvents with amide groups such as amide, N,N-dimethylacetamide, etc.; dimethyl sulfoxide.

烷、1,3-二氧雜環戊烷、4-甲基二氧雜環戊烷、四氫呋喃、甲基四氫呋喃、苯甲醚、苯乙醚等醚；乙腈、異丁腈、丙腈、甲氧基乙腈等具有腈基的有機溶劑；碳酸伸乙酯、碳酸伸丙酯等具有碳酸酯基的有機溶劑；二氯甲烷、氯仿等具有經鹵素化的烴基的有機溶劑；正戊烷、環己烷、正己烷、苯、甲苯、 二甲苯等具有烴基的有機溶劑。 The solvent used in the mixing step included in the aforementioned manufacturing method is preferably a solvent with low solubility of the semiconductor particles in the solvent. For example, when the aforementioned step is performed at room temperature (10°C to 30°C), methyl formate can be used , ethyl formate, propyl formate, amyl formate, methyl acetate, ethyl acetate, amyl acetate and other esters; γ-butyrolactone, N-methyl-2-pyrrolidone, acetone, dimethyl ketone , diisobutyl ketone, cyclopentanone, cyclohexanone, methyl cyclohexanone and other ketones; diethyl ether, methyl-tertiary-butyl ether, diisopropyl ether, dimethoxymethane, Dimethoxyethane, 1,4-dimethoxyethane

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

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

When the semiconductor fine particles are taken out from the dispersion liquid containing the semiconductor fine particles, only the semiconductor fine particles can be recovered by performing solid-liquid separation.

Examples of the aforementioned solid-liquid separation methods include methods such as filtration, methods using solvent evaporation, and the like.

<Second embodiment of the method for producing fine particles of perovskite compound crystals>

Hereinafter, the manufacturing method including the steps of adding components B, X, and A to a high-temperature solvent to dissolve them to obtain a solution, and a step of cooling the obtained solution will be described.

More specifically, for example, there may be mentioned a production method comprising the steps of adding a compound containing B component and X component, and a compound containing A component or A component and X component to a high temperature solvent, and dissolving it to obtain a solution. step; and the step of cooling the resulting solution.

In the aforementioned 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 difference in temperature.

The aforementioned manufacturing method preferably includes a step of adding a capping ligand from the viewpoint of stabilizing and dispersing the semiconductor fine particles.

The aforementioned manufacturing method preferably includes a step of removing coarse particles by means of centrifugation, filtration, etc. after the cooling step. The size of the coarse particles removed by the above-mentioned removing step is preferably 10 μm or more, more preferably 1 μm or more, and still more preferably 500 nm or more.

Here, the so-called high-temperature solvent should just be a solvent at a temperature at which the compound of component B and component X, and the compound containing component A or component A and X can be dissolved, for example, a solvent of 60 to 600° C. is preferable. , the solvent of 80 to 400 ℃ is better.

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

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

烷、1,3-二氧雜環戊烷、4-甲基二氧雜環戊烷、四氫呋喃、甲基四氫呋喃、苯甲醚、苯乙醚等醚；甲醇、乙醇、1-丙醇、2-丙醇、1-丁醇、2-丁醇、三級-丁醇、1-戊醇、2-甲基-2-丁醇、甲氧基丙醇、二丙酮醇、環己醇、2-氟乙醇、2,2,2-三氟乙醇、2,2,3,3-四氟-1-丙醇等醇；乙二醇單甲基醚、乙二醇單乙基醚、乙二醇單丁基醚、乙二醇單乙基醚乙酸酯、三乙二醇二甲基醚等二醇醚；N,N-二甲基甲醯胺、乙醯胺、N,N-二甲基乙醯胺等具有醯胺基的有機溶劑；乙腈、異丁腈、丙腈、甲氧基乙腈等具有腈基的有機溶劑；碳酸伸乙酯、碳酸伸丙酯等具有碳酸酯基的有機溶劑；二氯甲烷、氯仿等具有經鹵素化的烴基之有機溶劑；正戊烷、環己烷、正己烷、苯、甲苯、二甲苯等具有烴基的有機溶劑；二甲基亞碸、1-十八碳烯。 The solvent used in the above-mentioned production method is not particularly limited as long as it can dissolve the compound containing the B component and the X component, and the compound containing the A component or the A component and the X component, and examples thereof include methyl formate. Ester, ethyl formate, propyl formate, amyl formate, methyl acetate, ethyl acetate, amyl acetate and other esters; γ-butyrolactone, N-methyl-2-pyrrolidone, acetone, dimethyl Ketones, diisobutyl ketone, cyclopentanone, cyclohexanone, methyl cyclohexanone and other ketones; diethyl ether, methyl-tertiary-butyl ether, diisopropyl ether, dimethoxymethane , dimethoxyethane, 1,4-dimethoxyethane

alkane, 1,3-dioxolane, 4-methyldioxolane, tetrahydrofuran, methyltetrahydrofuran, anisole, phenethyl ether and other ethers; methanol, ethanol, 1-propanol, 2- Propanol, 1-butanol, 2-butanol, tertiary-butanol, 1-pentanol, 2-methyl-2-butanol, methoxypropanol, diacetone alcohol, cyclohexanol, 2- Alcohols such as fluoroethanol, 2,2,2-trifluoroethanol, 2,2,3,3-tetrafluoro-1-propanol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol Monobutyl ether, ethylene glycol monoethyl ether acetate, triethylene glycol dimethyl ether and other glycol ethers; N,N-dimethylformamide, acetamide, N,N-dimethyl ether Organic solvents with amide groups such as acetamide; organic solvents with nitrile groups such as acetonitrile, isobutyronitrile, propionitrile, and methoxyacetonitrile; organic solvents with carbonate groups such as ethylidene carbonate and propylidene carbonate Solvents; organic solvents with halogenated hydrocarbon groups such as dichloromethane and chloroform; organic solvents with hydrocarbon groups such as n-pentane, cyclohexane, n-hexane, benzene, toluene, and xylene; Octadecene.

As a method of taking out the semiconductor fine particles from the dispersion liquid containing the semiconductor fine particles, for example, a method of recovering only the semiconductor fine particles by performing solid-liquid separation is exemplified.

Examples of the aforementioned solid-liquid separation methods include methods such as filtration, methods using solvent evaporation, and the like.

<Production method of composition containing (1), (2) and (3)>

The method for producing a composition containing (1) semiconductor fine particles, (2) an organic compound having a hydrogen thiol group, and (3) at least one selected from the group consisting of a polymerizable compound and a polymer can be, for example, ( A method of mixing 1) semiconductor fine particles, (2) an organic compound having a hydrogen sulfide group, and (3) at least one selected from the group consisting of a polymerizable compound and a polymer.

At the time of mixing, it is preferable to mix with stirring from the viewpoint of improving dispersibility.

The mixing temperature is not particularly limited, but from the viewpoint of uniform mixing, it is preferably in the range of 0 to 100°C, more preferably in the range of 10 to 80°C.

For example, the production method of the composition of the present invention includes the following production method: (a) may be a production method comprising the following steps: (3) at least one selected from the group consisting of a polymerizable compound and a polymer is used. (1) a step of dispersing semiconductor fine particles to obtain a dispersion; and a step of mixing the obtained dispersion and (2) a step of an organic compound having a hydrogen thiol group; (6) a manufacturing method comprising the following steps: in (3) A step of dispersing (2) an organic compound having a thiosulfur group to obtain a dispersion; at least one selected from the group consisting of a polymerizable compound and a polymer; a step of mixing the obtained dispersion, and (1) a step of semiconductor fine particles (c) may be a manufacturing method comprising the following steps: (3) at least one selected from the group consisting of a polymerizable compound and a polymer to make (1) semiconductor fine particles and (2) a hydrogen sulfide group-containing The step of dispersing the mixture of organic compounds.

Among the production methods (a) to (c), the production method of (a) is preferred from the viewpoint of improving the dispersibility of the semiconductor fine particles. By the aforementioned method, the composition of the present invention can be obtained as (1) a dispersion in which semiconductor fine particles are dispersed in (3), and (2) a mixture of an organic compound having a hydrogen thiol group.

In the step of obtaining each dispersion included in the production methods of (a) to (c), (3) may be dropped into (1) and/or (2), or (1) and/or (2) may be added dropwise. ) dropwise into (3).

From the viewpoint of improving dispersibility, it is preferable to drop (1) and/or (2) into (3).

(1) or (2) may be dropped in the dispersion, or the dispersion may be dropped in (1) or (2) in each mixing step included in the production methods of (a) to (b).

From the viewpoint of improving dispersibility, it is preferable to drop (1) or (2) into the dispersion.

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

The solvent for dissolving the polymer is not particularly limited as long as it can dissolve the resin (polymer), but it is preferably one that hardly dissolves the semiconductor fine particles of the present invention.

烷、1,3-二氧雜環戊烷、4-甲基二氧雜環戊烷、四氫呋喃、甲基四氫呋喃、苯甲醚、苯乙醚等醚；甲醇、乙醇、1-丙醇、2-丙醇、1-丁醇、2-丁醇、三級-丁醇、1-戊醇、2-甲基-2-丁醇、甲氧基丙醇、二丙酮醇、環己醇、2-氟乙醇、2,2,2-三氟乙醇、2,2,3,3-四氟-1-丙醇等醇；乙二醇單甲基醚、乙二醇單乙基醚、乙二醇單丁基 醚、乙二醇單乙基醚乙酸酯、三乙二醇二甲基醚等二醇醚；N,N-二甲基甲醯胺、乙醯胺、N,N-二甲基乙醯胺等具有醯胺基的有機溶劑；乙腈、異丁腈、丙腈、甲氧基乙腈等具有腈基的有機溶劑；碳酸伸乙酯、碳酸伸丙酯等具有碳酸酯基的有機溶劑；二氯甲烷、氯仿等具有經鹵素化的烴基之有機溶劑；正戊烷、環己烷、正己烷、苯、甲苯、二甲苯等具有烴基的有機溶劑；二甲基亞碸。 The solvent that the above-mentioned resin dissolves can be exemplified by esters such as methyl formate, ethyl formate, propyl formate, amyl formate, methyl acetate, ethyl acetate, amyl acetate; γ-butyrolactone, N-methyl- 2-pyrrolidone, acetone, dimethyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methyl cyclohexanone and other ketones; diethyl ether, methyl-tertiary-butyl ether, Diisopropyl ether, dimethoxymethane, dimethoxyethane, 1,4-di

alkane, 1,3-dioxolane, 4-methyldioxolane, tetrahydrofuran, methyltetrahydrofuran, anisole, phenethyl ether and other ethers; methanol, ethanol, 1-propanol, 2- Propanol, 1-butanol, 2-butanol, tertiary-butanol, 1-pentanol, 2-methyl-2-butanol, methoxypropanol, diacetone alcohol, cyclohexanol, 2- Alcohols such as fluoroethanol, 2,2,2-trifluoroethanol, 2,2,3,3-tetrafluoro-1-propanol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol Monobutyl ether, ethylene glycol monoethyl ether acetate, triethylene glycol dimethyl ether and other glycol ethers; N,N-dimethylformamide, acetamide, N,N-dimethyl ether Organic solvents with amide groups such as acetamide; organic solvents with nitrile groups such as acetonitrile, isobutyronitrile, propionitrile, and methoxyacetonitrile; organic solvents with carbonate groups such as ethylidene carbonate and propylidene carbonate Solvents; organic solvents with halogenated hydrocarbon groups such as methylene chloride and chloroform; organic solvents with hydrocarbon groups such as n-pentane, cyclohexane, n-hexane, benzene, toluene, xylene, etc.; dimethylsulfite.

烷、1,3-二氧雜環戊烷、4-甲基二氧雜環戊烷、四氫呋喃、甲基四氫呋喃、苯甲醚、苯乙醚等醚；乙腈、異丁腈、丙腈、甲氧基乙腈等具有腈基的有機溶劑；碳酸伸乙酯、碳酸伸丙酯等碳酸酯系有機溶劑；二氯甲烷、氯仿等具有經鹵素化的烴基之有機溶劑；正戊烷、環己烷、正己烷、苯、甲苯、二甲苯等具有烴基的有機溶劑係極性低，咸認為難以溶解本發明相關的鈣鈦礦化合物，故較佳，二氯甲烷、氯仿等具有經鹵素化的烴基之有機溶劑；正戊烷、環己烷、正己烷、苯、甲苯、二甲苯等具有烴基的有機溶劑為更佳。 Among them, methyl formate, ethyl formate, propyl formate, amyl formate, methyl acetate, ethyl acetate, amyl acetate and other esters; γ-butyrolactone, acetone, dimethyl ketone, diisobutyl Ketones such as ketone, cyclopentanone, cyclohexanone, methylcyclohexanone; diethyl ether, methyl-tertiary-butyl ether, diisopropyl ether, dimethoxymethane, dimethoxyethyl ether Alkane, 1,4-di

alkane, 1,3-dioxolane, 4-methyldioxolane, tetrahydrofuran, methyltetrahydrofuran, anisole, phenethyl ether and other ethers; acetonitrile, isobutyronitrile, propionitrile, methoxy Organic solvents with nitrile groups such as acetonitrile; carbonate-based organic solvents such as ethylidene carbonate and propylidene carbonate; organic solvents with halogenated hydrocarbon groups such as dichloromethane and chloroform; n-pentane, cyclohexane, Organic solvents with hydrocarbon groups such as n-hexane, benzene, toluene, and xylene are low in polarity, and it is considered difficult to dissolve the perovskite compounds related to the present invention. Therefore, organic solvents with halogenated hydrocarbon groups such as dichloromethane and chloroform are preferred. Solvents; organic solvents with hydrocarbon groups such as n-pentane, cyclohexane, n-hexane, benzene, toluene and xylene are more preferred.

<Production method of composition containing (1), (2), (3) and (4)>

Contains (1) semiconductor fine particles, (2) an organic compound having a hydrogen thio group, (3) at least one selected from the group consisting of a polymerizable compound and a polymer, and (4) selected from ammonia, an amine, and The method for producing a composition of a carboxylic acid and at least one selected from the group of salts or ions of these may include addition (4) selected from the group consisting of ammonia, amines, and carboxylic acids, and salts or ions of these. Except for at least 1 type in a group, the manufacturing method of the above-mentioned composition containing (1), (2) and (3) may be the same.

(4) At least one species selected from the group consisting of ammonia, amines, and carboxylic acids, and salts or ions thereof may be added in any step included in the above-mentioned (1) semiconductor fine particle manufacturing method, or may be added. It is added in any step included in the method for producing a composition containing (1), (2) and (3) above.

(4) At least one selected from the group consisting of ammonia, amines, and carboxylic acids, and salts or ions of these, from the viewpoint of improving the dispersibility of the semiconductor fine particles, used in the production of (1) semiconductor fine particles Any steps included in the method are preferably added. Thereby, for example, (1) semiconductor fine particles containing (4) at least one selected from the group consisting of ammonia, amines, and carboxylic acids, and salts or ions of these, are dispersed in (3) selected from The composition according to the present invention can be obtained by a dispersion of at least one of the polymerizable compound and the polymer group and a mixture of (2) an organic compound having a thiol group.

<Production method of a composition containing the composition of (1), (2) and (3'), and the total of (1), (2) and (3') is 90% by mass or more>

The production method of the composition containing (1), (2) and (3') and the total of (1), (2) and (3') is 90% by mass or more, for example, includes the following production methods: A step of mixing (1) semiconductor fine particles, (2) an organic compound having a thiosulfur group, and a polymerizable compound; and a step of polymerizing the polymerizable compound; and mixing (1) semiconductor fine particles, (2) a compound having a sulfhydryl group The organic compound, and the step of dissolving the polymer in the solvent, and the step of removing the solvent.

The step of mixing included in the above-mentioned production method can be used as described above with (1) semiconductor fine particles and (2) an organic compound having a hydrogen sulfide group, and (3) a compound selected from the group consisting of a polymerizable compound and a polymer. The mixing method is the same as the manufacturing method of the composition of at least 1 type in a group.

The aforementioned manufacturing method is, for example,

(a1) may be a production method comprising the steps of: dispersing (1) semiconductor fine particles in a polymerizable compound to obtain a dispersion; and mixing the obtained dispersion and (2) an organic compound having a hydrogen sulfide group; and the step of polymerizing the polymerizable compound.

(a2) may be a manufacturing method comprising the steps of: dispersing (1) semiconductor fine particles in a polymer dissolved in a solvent to obtain a dispersion; mixing the resulting dispersion and (2) an organic compound having a hydrogen sulfide group and the step of removing the solvent.

(b1) may be a manufacturing method comprising the steps of: dispersing (2) an organic compound having a thiosulfur group in a polymerizable compound to obtain a dispersion; mixing the obtained dispersion; and (1) a step of semiconductor fine particles ; and the step of polymerizing the polymerizable compound.

(b2) may be a production method comprising the steps of: dispersing (2) an organic compound having a thiosulfur group in a polymer dissolved in a solvent to obtain a dispersion; mixing the obtained dispersion and (1) a semiconductor the step of microparticles; and the step of removing the solvent.

(c1) may be a production method comprising the steps of: dispersing a mixture of (1) semiconductor fine particles and (2) an organic compound having a thiol group in a polymerizable compound; and polymerizing the polymerizable compound.

(c2) may be a production method comprising the steps of: dispersing a mixture of (1) semiconductor fine particles and (2) an organic compound having a thiol group in a polymer dissolved in a solvent; and removing the solvent.

The step of removing the solvent included in the above-mentioned production method may be a step of standing at room temperature to dry naturally, or a step of evaporating the solvent by drying under reduced pressure using a vacuum dryer or heating.

For example, it may be dried at 0 to 300° C. for 1 minute to 7 days to remove the solvent.

The step of polymerizing the polymerizable compound included in the above-mentioned production method can be appropriately performed using a known polymerization reaction such as radical polymerization.

For example, in the case of radical polymerization, a radical polymerization initiator can be added to a mixture of (1) semiconductor fine particles, (2) an organic compound having a thiosulfuryl group, and a polymerizable compound to generate radicals to carry out the polymerization reaction.

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

As said photoradical polymerization initiator system, bis(2,4,6-trimethylbenzyl)-phenylphosphine oxide etc. are mentioned, for example.

<Method for producing a composition containing (1), (2), (3') and (4) and the total of (1), (2), (3') and (4) is 90% by mass or more>

Contains (1) semiconductor microparticles, (2) organic compounds having thiol groups, (3') polymers, and (4) selected from the group consisting of ammonia, amines and carboxylic acids, and salts or ions of these A method for producing at least one composition of which the total of (1), (2), (3') and (4) is 90% by mass or more, except adding (4) selected from the group consisting of ammonia, amine and carboxyl In addition to at least one of the group consisting of an acid, a salt or an ion of these, it may contain (1), (2) and (3') and (1), (2) and (3) as described above. ') is the same as the method for producing the composition in which the total amount is 90% by mass or more.

(4) At least one selected from the group consisting of ammonia, amines, and carboxylic acids, and salts or ions of these, may be added in any step included in the above-mentioned (1) method for producing semiconductor fine particles, or It can be added in the step of mixing the above-mentioned (1) semiconductor fine particles, (2) organic compound having a thiosulfur group, and a polymerizable compound, and can be added after mixing the above (1) semiconductor fine particles, (2) organic compound having a sulfhydryl group. The compound and the polymer dissolved in the solvent are added in steps.

(5) At least one selected from the group consisting of ammonia, amines, carboxylic acids, and salts or ions of these, preferably in the production of (1) semiconductor fine particles from the viewpoint of improving the dispersibility of semiconductor fine particles Any step included in the method is added.

≪Measurement of Semiconductor Microparticles≫

The amount of the semiconductor fine particles contained in the composition according to the present invention is measured using ICP-MS (eg, ELAN DRCII, manufactured by Perkin Elmer) and ion chromatography.

Measurement is performed by dissolving semiconductor fine particles in 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 (eg, Hamamatsu Photonics, trade name C9920-02) under excitation light of 450 nm, room temperature, and atmosphere.

(1) In a composition containing semiconductor fine particles and (2) an organic compound having a hydrogen thio group, and (3) at least one selected from the group consisting of a polymerizable compound and a polymer, the composition is The mixture ratio was adjusted so that the concentration of the semiconductor fine particles contained in the material was 1000 μg/mL, and the measurement was carried out. The same applies when (3) is substituted with (3').

The quantum yield of the composition of the present embodiment measured by the above-mentioned measurement method is 32% or more, 40% or more, 50% or more, 60% or more, or 70% or more.

The quantum yield of the composition of the present embodiment measured by the above-mentioned measuring method is 100% or less, 95% or less, 90% or less, or 80% or less.

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

In one aspect of the present invention, the quantum yield of the composition of this embodiment measured by the above-mentioned measuring method is preferably 32% or more and 100% or less, more preferably 40% or more and 100% or less, and 50%. More than 100% is the best, and more than 70% and less than 100% is the best.

In another aspect of the present invention, the quantum yield of the composition of this embodiment measured by the above-mentioned measuring method is preferably 32% or more and 95% or less, more preferably 40% or more and 90% or less, and 50% or more. % above 80% is the best. In addition, the quantum yield may be 60% or more and 80% or less, or 70% or more and 80% or less.

<film>

The film system according to the present invention contains (1), (2), and (3'), and a composition in which the total content of (1), (2), and (3') is 90% by mass or more relative to the total mass of the composition film made of matter.

(1) Semiconductor fine particles

(2) Organic compounds having a hydrogen thiol group

(3') polymer

The shape of the film is not particularly limited, and may be a sheet shape, a rod shape, or the like. The term "rod-like shape" in this specification means, for example, a shape having anisotropy. The shape having anisotropy can be exemplified by a plate-like shape in which the lengths of each side are different.

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

In this specification, the thickness of the said film is obtained by measuring arbitrary 3 points by a micrometer, and calculating the average value.

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

A film formed on a substrate can be obtained by, for example, the manufacturing methods (i) to (iii) of the later-described manufacturing methods of the laminated structure.

<Layered Structure>

The laminated structure system according to the present invention has a plurality of layers, and at least one layer is a composition containing (1), (2) and (3'), and the total content of (1), (2) and (3') is relatively A layered structure of layers composed of a composition in which the total mass of the composition is 90% by mass or more.

(1) Semiconductor fine particles

(2) Organic compounds having a hydrogen thiol group

(3') polymer

The composition containing (1), (2) and (3') may further contain (4) at least one selected from the group consisting of ammonia, amine and carboxylic acid, and salts or ions of these.

The laminated structure has a plurality of layers that contain (1), (2) and (3') and the total content of (1), (2) and (3') is 90% by mass or more relative to the total mass of the composition The layer other than the layer constituted by the composition includes, for example, any layer such as a substrate, a barrier layer, and a light scattering layer.

The shape of the composition to be laminated is not particularly limited, and may be any shape such as a flake shape or a rod shape. The laminated composition may also be the film of this embodiment.

(substrate)

The layer system that the laminated structure according to the present invention can have is not particularly limited, and examples thereof include a substrate.

The substrate system is not particularly limited, and may be a film, and a transparent one is preferred from the viewpoint of taking out light during light emission. As a board|substrate, well-known materials, such as plastics, such as polyethylene terephthalate, and glass, can be used, for example.

For example, the laminated structure contains (1), (2) and (3') and the total content of (1), (2) and (3') is 90% by mass or more with respect to the total mass of the composition. The layers formed by the composition can be provided on the substrate.

The aforementioned layer may also be the film of this embodiment.

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

The laminated structure 1a of one aspect of the present invention is characterized by having a first substrate 20, a second substrate 21, the film 10 according to the present embodiment positioned between the first substrate 20 and the second substrate 21, and a sealing layer In the laminated structure of 22, the sealing layer is disposed on the surface of the film 10 which is not in contact with the first substrate 20 and the second substrate 21.

(barrier layer)

The layer system that the laminated structure according to the present invention can have is not particularly limited, and examples thereof include barrier layers. In order to protect the aforementioned composition from water vapor in the outside air and air in the atmosphere, a barrier layer may also be included.

The barrier layer is not particularly limited, but from the viewpoint of extracting light after emission, a transparent barrier layer is preferred. For example, known barrier layers such as polymers such as polyethylene terephthalate and glass films can be applied.

(light scattering layer)

The layer system that the laminated structure according to the present invention can have is not particularly limited, and examples thereof include a light scattering layer. From the viewpoint of efficiently absorbing incident light, a light scattering layer may be included.

The light-scattering layer is not particularly limited, and from the viewpoint of extracting light after light emission, a transparent light-scattering layer is preferred. For example, known light-scattering layers such as light-scattering particles such as silicon oxide particles and amplification diffusion films can be used. .

<Manufacturing method of laminated structure>

Examples of the method for producing a layered structure include (i) a method for producing a layered structure comprising the steps of dissolving (1) semiconductor fine particles and (2) a polymer obtained by dissolving an organic compound having a hydrogen sulfide group in a solvent The step of mixing; the step of applying the obtained composition on the substrate; the step of removing the solvent; (ii) the method of manufacturing a laminated structure comprising the steps of: (1), (2) and (3') ), and the step of attaching the composition of (1), (2) and (3') in total of 90% by mass or more to the substrate; (1) semiconductor fine particles, (2) organic thiol group compound, (3') polymer; (iii) a method for producing a layered structure comprising the steps of mixing (1) semiconductor fine particles, (2) an organic compound having a thiol group, and a polymerizable compound; A step of 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 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) may be the same as those described above. (1), (2) and (3'), and (1), (2) and (3') are the same steps as the steps included in the manufacturing method of the composition in which the total of (1), (2) and (3') is 90% by mass or more.

The steps of coating on the substrate included in the manufacturing methods (i) and (iii) are particularly limited, but a gravure coating method, a rod coating method, a printing method, a spray coating method, a spin coating method, a dipping method, A known coating method such as a die-slot coating method is used.

Arbitrary adhesives can be used in the step of bonding to a board|substrate contained in the manufacturing method of (ii).

The adhesive agent is not particularly limited as long as it does not dissolve the semiconductor fine particles (1), and known adhesive agents can be used.

The manufacturing method of a laminated structure is a manufacturing method which can further include the process of attaching arbitrary films to the laminated structure obtained by (i)-(iii).

The film system to be bonded includes, for example, a reflective film and a diffusion film.

In the step of laminating the film, any adhesive can be used.

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

<Light-emitting device>

The light-emitting device according to the present invention can be obtained by combining the above-mentioned composition, or the above-mentioned laminated structure, and a light source. The light-emitting device according to the present invention is a device that emits light from a light source to the composition provided in the latter stage to emit light and extracts the light. The layered structure in the aforementioned light-emitting device may include layers such as a reflective film, a diffusion film, a brightness enhancement portion, a wafer, a light guide plate, and a dielectric material layer between members.

One aspect of the present invention is a light-emitting device 2 formed by sequentially laminating a wafer 50 , a light guide plate 60 , the aforementioned first laminated structure 1 a , and a light source 30 .

(light source)

The light source constituting the light-emitting device in the present invention is not particularly limited, but from the viewpoint of emitting light from the aforementioned composition or the semiconductor fine particles in the laminated structure, a light source having an emission wavelength of 600 nm or less is preferable, for example, A well-known light source such as a light emitting diode (LED) such as a blue light emitting diode, a laser, and an EL can be used.

(Reflective film)

The light-emitting device according to the present invention is not particularly limited, but may include a light reflecting member for irradiating the light from the light source toward the aforementioned composition or the aforementioned laminated structure.

The reflective film is not particularly limited, but may include any appropriate known material such as a mirror, a film of reflective particles, a reflective metal film, or a reflector.

(diffusion film)

The light-emitting device related to the present invention is not particularly limited, but may include a light-scattering member for diffusing light from a light source or light emitted from the aforementioned composition. The diffusion membrane system may include any diffusion membrane known in the aforementioned technical field, such as an amplification diffusion membrane.

(brightness enhancement part)

The light-emitting device related to the present invention is not particularly limited, but may include a brightness enhancement portion in which a part of the light is reflected toward the direction in which the light is transmitted and returned.

(Jihan Tablet)

A typical high-end tablet has a base material part and a high-end surface part. In addition, the base material part can be omitted according to the adjoining member. The wafer can be attached to the adjoining members via any appropriate adhesive layer (eg, adhesive layer, adhesive layer). The rim plate is juxtaposed with a plurality of unit rims whose identification side is the opposite side (back side) to form a protrusion. By arranging the convex portion of the iris sheet toward the back side, the light passing through the iris sheet is easily condensed. In addition, when the convex portion of the iris sheet is arranged toward the back side, compared with arranging the convex portion toward the recognition side, less light is reflected without incident on the iris sheet, and a display with high brightness can be obtained.

(light guide plate)

Any suitable light guide plate can be used for the light guide plate system. For example, it can be used for a light guide plate in which a lens pattern is formed on the back side, a light guide plate in which a zigzag shape is formed on the back side and/or the recognition side, etc., so that the light from the lateral direction can be deflected in the thickness direction.

(dielectric material layer between components)

The light-emitting device related to the present invention is not particularly limited, and may include one or more layers composed of dielectric materials on the optical path between adjacent members (layers). More than one medium system includes vacuum, air, gas, optical material, adhesive, optical adhesive, glass, polymer, solid, liquid, gel, hardened material, optical adhesive material, refractive index integration or refractive index unintegration Materials, refractive index gradient materials, overlay or anti-overlay materials, spacers, silica gels, brightness enhancing materials, scattering or diffusing materials, reflective or anti-reflective materials, wavelength selective materials, wavelength selective anti-reflective materials, color filters Sheets, or other suitable media known in the aforementioned technical field, but are not limited to these, and may also include any suitable materials.

A specific example of the light-emitting device according to the present invention includes, for example, a wavelength conversion material for an EL display or a liquid crystal display.

Specifically, for example: (1) The composition of the present invention is placed in a glass tube, etc. and sealed, and the blue light-emitting diode of the light source and the guide are arranged along the end surface (side surface) of the light guide plate. Between the light plates, a backlight that converts blue light into green light or red light (backlight of side-illumination mode), (2) The composition related to the present invention is thinned, and this is sandwiched and sealed with two barrier films. The film is arranged on the light guide plate, and the blue light irradiated from the blue light-emitting diode placed on the end face (side) of the light guide plate to the aforementioned sheet through the light guide plate is converted into a backlight of green light or red light (the one of the surface encapsulation method) Backlight), (3) A backlight (on-chip) that disperses semiconductor fine particles in resin, etc., and is arranged near the light-emitting part of the blue light-emitting diode, and converts the irradiated blue light into green light or red light (on-chip) Backlight of the method), and (4) a backlight in which semiconductor fine particles are dispersed in a resist and placed on a color filter to convert blue light irradiated from a light source into green or red light.

In addition, a specific example of the light-emitting device according to the present invention may include, for example, molding the composition of the present invention, disposing it in the rear stage of the blue light-emitting diode of the light source, converting blue light into green light or red light, and emitting white light. illumination.

<Manufacturing method of light-emitting device>

For example, a manufacturing method including the step of disposing the above-mentioned light source and the optical path from the light source to the rear stage of the above-mentioned composition or laminated structure can be mentioned.

<Display>

As shown in FIG. 2, the display 3 of the present embodiment includes a liquid crystal panel 40 and the aforementioned light-emitting device 2 in this order from the recognition side. The light-emitting device 2 includes the second laminated structure 1 b and the light source 30 . The second layered structure 1b is the one further provided with the above-mentioned first layered structure 1a including the iris sheet 50 and the light guide plate 60 . The liquid crystal panel typically includes a liquid crystal cell, a recognition-side polarizer arranged on the recognition side of the liquid crystal cell, and a rear-side polarizer arranged on the rear side of the liquid crystal cell. The display system may further comprise any suitable other components.

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

<Liquid crystal panel>

The above-mentioned liquid crystal panel typically includes a liquid crystal cell, an identification-side polarizer disposed on the identification side of the liquid crystal cell, and a rear-side polarizer disposed on the rear side of the liquid crystal cell. The recognition side polarizer and the back side polarizer can have their respective absorption axes arranged in a substantially orthogonal or parallel manner.

(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 structure, one substrate is provided with a color filter and a black matrix, and the other substrate is provided with a switch element for regulating the electrical and optical properties of the liquid crystal, a scan line for imparting a gate signal to the switch element, and The signal line of the source signal, the pixel electrode and the opposite electrode. The space between the substrates (cell gap) can be adjusted by spacers or the like. The side which is in contact with the liquid crystal layer of the above-mentioned substrate may be provided with, for example, an alignment film made of polyimide.

(Polarizer)

A polarizer typically has a polarizer and a protective layer disposed on both sides of the polarizer. The representative polarizer is an absorption polarizer.

Any appropriate polarizer can be used for the above-mentioned polarizer system. For example, dichroism that adsorbs iodine or dichroic dyes on hydrophilic polymer films such as polyvinyl alcohol-based films, partially formaldehyde-based polyvinyl alcohol-based films, and ethylene/vinyl acetate copolymer-based partially saponified films uniaxially stretched materials; polyolefin-based oriented films such as dehydration-treated products of polyvinyl alcohol or dehydrochloric acid-treated products of polyvinyl chloride, etc. Among these, the polarizer which adsorb|sucks a dichroic substance, such as iodine in a polyvinyl alcohol-type film, and is uniaxially stretched has a high polarized light dichroism ratio, and is especially preferable.

The composition of the present invention can be used as a wavelength conversion material for laser diodes, for example.

<LED>

The composition related to the present invention can be used, for example, as the material of the LED light-emitting layer.

The LED system containing the composition according to the present invention includes, for example, the composition according to the present invention and conductive particles such as ZnS and other conductive particles are mixed and laminated in the form of a film, an n-type transport layer is formed on a single surface, and a p-type transport layer is formed on one side. In the laminated structure, when a current flows, the holes of the p-type semiconductor and the electrons of the n-type semiconductor destroy the electric charges in the semiconductor fine particles contained in the composition of the junction surface to emit light.

<Solar battery>

The composition according to the present invention can be used as an electron transport material contained in an active layer of a solar cell.

The structure of the aforementioned solar cell is not particularly limited, and examples include, for example, a tin oxide (FTO) substrate doped with fluorine, a titanium oxide dense layer, a porous alumina layer, an active layer containing the composition according to the present invention, 2 , 2',7,7'-4-(N,N'-di-p-methoxyphenylamine)-9,9'-spirobispyridine (spiro-OMeTAD) and other hole transport layers, and silver (Ag) electrodes for solar cells.

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

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

The composition according to the present invention contained in the active layer plays the role of charge separation and electron transport.

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

[Example]

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

(Synthesis of Components)

[Example 1]

0.814 g of cesium carbonate, 40 mL of a solvent for 1-octadecene, and 2.5 mL of oleic acid were mixed. A cesium carbonate solution was prepared by heating at 150 degreeC for 1 hour, stirring with a magnetic stirring bar, flowing nitrogen gas.

0.276 g of lead bromide ( _{PbBr 2} ) was mixed with 20 mL of a solvent for 1-octadecene. After stirring with a magnetic stirrer and heating at a temperature of 120° C. for 1 hour while flowing nitrogen, 2 mL of oleic acid and 2 mL of oleylamine were added. After the temperature was raised to 160° C., 1.6 mL of the above-mentioned cesium carbonate solution was added. After the addition, the reaction vessel was immersed in ice water and cooled to room temperature.

Then, the dispersion liquid was centrifuged at 10,000 rpm for 5 minutes to separate the precipitate, and the precipitated semiconductor fine particles were obtained.

The X-ray diffraction pattern of the semiconductor fine particles was measured with an X-ray diffraction measuring apparatus (XRD, Cu Kα ray, X'pert PRO MPD, manufactured by Spectris Corporation), and as a result, it was confirmed that there is an X-ray diffraction pattern at the position of 2θ=14°. (hkl)=(001) peak, and has a 3-dimensional perovskite crystal structure.

The average Feret diameter of the perovskite compound after observation 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 liquid was divided and dispersed in 4.5 mL of toluene to obtain a dispersion liquid containing semiconductor fine particles and a solvent. The perovskite compound concentration measured by ICP-MS and ion chromatography was 1500 ppm (μg/g).

Then, after mixing with toluene so that methacrylic resin (PMMA, manufactured by Sumitomo Chemical Co., Ltd., Sumipex/methacrylic resin, MH, molecular weight about 120,000, specific gravity 1.2 g/ml) would be 16.5 mass %, it was heated at 60°C After 3 hours, a solution after the polymer was dissolved was obtained.

After mixing 0.15 g of the above-mentioned dispersion liquid containing semiconductor fine particles and a solvent, and 0.913 g of the polymer-dissolved solution, in a cup made of aluminum so that the molar ratio becomes 1-hexadecanethiol/Pb=4.89 (4.5φcm) mixed.

Toluene was evaporated by natural drying to obtain a composition having a perovskite compound concentration of 1000 μg/mL. The composition was cut into a size of 1 cm x 1 cm.

[Example 2]

A composition was obtained in the same manner as in Example 1 above except that 1-hexadecanethiol/Pb=24.4.

[Example 3]

A composition was obtained in the same manner as in Example 1 above except that 1-hexadecanethiol/Pb=48.9.

[Example 4]

A composition was obtained in the same manner as in Example 1 above except that 1-hexadecanethiol/Pb=147.

[Example 5]

0.814 g of cesium carbonate, 40 mL of a solvent for 1-octadecene, and 2.5 mL of oleic acid were mixed. A cesium carbonate solution was prepared by heating at 150 degreeC for 1 hour, stirring with a magnetic stirring bar, flowing nitrogen gas.

0.276 g of lead bromide ( _{PbBr 2} ) was mixed with 20 mL of a solvent for 1-octadecene. After stirring with a magnetic stirrer and heating at a temperature of 120° C. for 1 hour while flowing nitrogen, 2 mL of oleic acid and 2 mL of oleylamine were added. After the temperature was raised to 160° C., 1.6 mL of the above-mentioned cesium carbonate solution was added. After the addition, the reaction vessel was immersed in ice water and cooled to room temperature.

Then, the dispersion liquid was centrifuged at 10,000 rpm for 5 minutes to separate the precipitate, and the precipitated semiconductor fine particles were obtained.

The X-ray diffraction pattern of the semiconductor fine particles was measured with an X-ray diffraction measuring apparatus (XRD, Cu Kα ray, X'pert PRO MPD, manufactured by Spectris Corporation), and as a result, it was confirmed that at the position of 2θ=14°, there was a (hkl)=(001) peak, and has a 3-dimensional perovskite crystal structure.

The average Feret diameter of the perovskite compound after observation 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 liquid was divided and dispersed in 4.5 mL of toluene to obtain a dispersion liquid containing semiconductor fine particles and a solvent. The perovskite compound concentration measured by ICP-MS and ion chromatography was 1500 ppm (μg/g).

Then, after mixing with toluene so that methacrylic resin (PMMA, manufactured by Sumitomo Chemical Co., Ltd., Sumipex/methacrylic resin, MH, molecular weight about 120,000, specific gravity 1.2 g/ml) would be 16.5 mass %, it was heated at 60°C After 3 hours, a solution after the polymer was dissolved was obtained.

After mixing 0.15 g of the above-mentioned dispersion liquid containing semiconductor fine particles and a solvent, and 0.913 g of the solution after dissolving the polymer, in an aluminum cup ( 4.5φcm) mixed.

Toluene was evaporated by natural drying to obtain a composition having a perovskite compound concentration of 1000 μg/mL. The composition was cut into a size of 1 cm x 1 cm.

[Example 6]

A composition was obtained in the same manner as in Example 5 above except that 1-decanethiol/Pb=72.1.

[Example 7]

A composition was obtained in the same manner as in Example 5 above except that 1-decanethiol/Pb=144.

[Example 8]

0.814 g of cesium carbonate, 40 mL of a solvent for 1-octadecene, and 2.5 mL of oleic acid were mixed. A cesium carbonate solution was prepared by heating at 150 degreeC for 1 hour, stirring with a magnetic stirring bar, flowing nitrogen gas.

0.276 g of lead bromide ( _{PbBr 2} ) was mixed with 20 mL of a solvent for 1-octadecene. After stirring with a magnetic stirrer and heating at a temperature of 120° C. for 1 hour while flowing nitrogen, 2 mL of oleic acid and 2 mL of oleylamine were added. After the temperature was raised to 160° C., 1.6 mL of the above-mentioned cesium carbonate solution was added. After the addition, the reaction vessel was immersed in ice water and cooled to room temperature.

Then, the dispersion liquid was centrifuged at 10,000 rpm for 5 minutes to separate the precipitate, and the precipitated semiconductor fine particles were obtained.

The X-ray diffraction pattern of the semiconductor fine particles was measured with an X-ray diffraction measuring apparatus (XRD, Cu Kα ray, X'pert PRO MPD, manufactured by Spectris Corporation), and as a result, it was confirmed that at the position of 2θ=14°, there was a (hkl)=(001) peak, and has a 3-dimensional perovskite crystal structure.

The average Feret diameter of the perovskite compound after observation 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 liquid was divided and dispersed in 4.5 mL of toluene to obtain a dispersion liquid containing semiconductor fine particles and a solvent. The perovskite compound concentration measured by ICP-MS and ion chromatography was 1500 ppm (μg/g).

Then, after mixing with toluene so that methacrylic resin (PMMA, manufactured by Sumitomo Chemical Co., Ltd., Sumipex/methacrylic resin, MH, molecular weight about 120,000, specific gravity 1.2 g/ml) would be 16.5 mass %, it was heated at 60°C After 3 hours, a solution after the polymer was dissolved was obtained. After mixing 0.15 g of the above-mentioned dispersion liquid containing semiconductor fine particles and a solvent, and 0.913 g of the solution after dissolving the polymer, the solution was mixed in a molar ratio of 1-docosanethiol/Pb=13.1. Mix in a cup (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 into a size of 1 cm x 1 cm.

[Example 9]

A composition was obtained in the same manner as in Example 8 above except that 1-docosanethiol/Pb=43.6.

[Example 10]

0.814 g of cesium carbonate, 40 mL of a solvent for 1-octadecene, and 2.5 mL of oleic acid were mixed. A cesium carbonate solution was prepared by heating at 150 degreeC for 1 hour, stirring with a magnetic stirring bar, flowing nitrogen gas.

0.276 g of lead bromide ( _{PbBr 2} ) was mixed with 20 mL of a solvent for 1-octadecene. After stirring with a magnetic stirrer and heating at a temperature of 120° C. for 1 hour while flowing nitrogen, 2 mL of oleic acid and 2 mL of oleylamine were added. After the temperature was raised to 160° C., 1.6 mL of the above-mentioned cesium carbonate solution was added. After the addition, the reaction vessel was immersed in ice water and cooled to room temperature.

Then, the dispersion liquid was centrifuged at 10,000 rpm for 5 minutes to separate the precipitate, and the precipitated semiconductor fine particles were obtained.

The X-ray diffraction pattern of the semiconductor fine particles was measured with an X-ray diffraction measuring apparatus (XRD, Cu Kα ray, X'pert PRO MPD, manufactured by Spectris Corporation), and as a result, it was confirmed that at the position of 2θ=14°, there was a (hkl)=(001) peak, and has a 3-dimensional perovskite crystal structure.

The average Feret diameter of the perovskite compound after observation 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 liquid was divided and dispersed in 4.5 mL of toluene to obtain a dispersion liquid containing semiconductor fine particles and a solvent. The perovskite compound concentration measured by ICP-MS and ion chromatography was 1500 ppm (μg/g).

Then, after mixing with toluene so that methacrylic resin (PMMA, manufactured by Sumitomo Chemical Co., Ltd., Sumipex/methacrylic resin, MH, molecular weight about 120,000, specific gravity 1.2 g/ml) would be 16.5 mass %, it was heated at 60°C After 3 hours, a solution after the polymer was dissolved was obtained. After mixing 0.15 g of the above-mentioned dispersion liquid containing semiconductor fine particles and a solvent, and 0.913 g of the solution after dissolving the polymer, the solution was mixed with 1,10-decanedithiol/Pb=20.7 in a molar ratio. Mix in the cup (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 into a size of 1 cm x 1 cm.

[Example 11]

A composition was obtained in the same manner as in Example 10 above except that 1,10-decanedithiol/Pb=68.9.

[Example 12]

A composition was obtained in the same manner as in Example 10 above except that 1,10-decanedithiol/Pb=138.

[Example 13]

0.814 g of cesium carbonate, 40 mL of a solvent for 1-octadecene, and 2.5 mL of oleic acid were mixed. A cesium carbonate solution was prepared by heating at 150 degreeC for 1 hour, stirring with a magnetic stirring bar, flowing nitrogen gas.

0.276 g of lead bromide ( _{PbBr 2} ) was mixed with 20 mL of a solvent for 1-octadecene. After stirring with a magnetic stirrer and heating at a temperature of 120° C. for 1 hour while flowing nitrogen, 2 mL of oleic acid and 2 mL of oleylamine were added. After the temperature was raised to 160° C., 1.6 mL of the above-mentioned cesium carbonate solution was added. After the addition, the reaction vessel was immersed in ice water and cooled to room temperature.

Then, the dispersion liquid was centrifuged at 10,000 rpm for 5 minutes to separate the precipitate, and the precipitated semiconductor fine particles were obtained.

The X-ray diffraction pattern of the semiconductor fine particles was measured with an X-ray diffraction measuring apparatus (XRD, Cu Kα ray, X'pert PRO MPD, manufactured by Spectris Corporation), and as a result, it was confirmed that at the position of 2θ=14°, there was a (hkl)=(001) peak, and has a 3-dimensional perovskite crystal structure.

The average Feret diameter of the perovskite compound after observation 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 liquid was divided and dispersed in 4.5 mL of toluene to obtain a dispersion liquid containing semiconductor fine particles and a solvent. The perovskite compound concentration measured by ICP-MS and ion chromatography was 1500 ppm (μg/g).

Then, after mixing with toluene so that methacrylic resin (PMMA, manufactured by Sumitomo Chemical Co., Ltd., Sumipex/methacrylic resin, MH, molecular weight about 120,000, specific gravity 1.2 g/ml) would be 16.5 mass %, it was heated at 60°C After 3 hours, a solution after the polymer was dissolved was obtained. After mixing 0.15 g of the dispersion liquid containing the semiconductor fine particles and the solvent and 0.913 g of the solution after dissolving the polymer, the molar ratio was 3-(trimethoxysilyl)propanethiol/Pb=24.2. Mix in an aluminum cup (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 into a size of 1 cm x 1 cm.

[Example 14]

A composition was obtained in the same manner as in Example 13 above except that 3-(trimethoxysilyl)propanethiol/Pb=80.8.

[Comparative Example 1]

0.814 g of cesium carbonate, 40 mL of a solvent for 1-octadecene, and 2.5 mL of oleic acid were mixed. A cesium carbonate solution was prepared by heating at 150 degreeC for 1 hour, stirring with a magnetic stirring bar, flowing nitrogen gas.

0.276 g of lead bromide ( _{PbBr 2} ) was mixed with 20 mL of a solvent for 1-octadecene. After stirring with a magnetic stirrer and heating at a temperature of 120° C. for 1 hour while flowing nitrogen, 2 mL of oleic acid and 2 mL of oleylamine were added. After the temperature was raised to 160° C., 1.6 mL of the above-mentioned cesium carbonate solution was added. After the addition, the reaction vessel was immersed in ice water and cooled to room temperature.

Then, the dispersion liquid was centrifuged at 10,000 rpm for 5 minutes to separate the precipitate, and the precipitated semiconductor fine particles were obtained.

The X-ray diffraction pattern of the semiconductor fine particles was measured with an X-ray diffraction measuring apparatus (XRD, Cu Kα ray, X'pert PRO MPD, manufactured by Spectris Corporation), and as a result, it was confirmed that at the position of 2θ=14°, there was a (hkl)=(001) peak, and has a 3-dimensional perovskite crystal structure.

The average Feret diameter of the perovskite compound after observation by TEM (manufactured by JEOL Ltd., JEM-2200FS) was 11 nm.

After dispersing the semiconductor fine particles in 5 mL of toluene, 50 µL of the dispersion liquid was aliquoted and dispersed in 4.5 mL of toluene to obtain a dispersion liquid containing semiconductor fine particles and a solvent. The concentration of the perovskite compound measured by ICP-MS and ion chromatography was 1000 μg/mL.

Then, after mixing with toluene so that methacrylic resin (PMMA, manufactured by Sumitomo Chemical Co., Ltd., Sumipex/methacrylic resin, MH, molecular weight about 120,000, specific gravity 1.2 g/ml) would be 16.5 mass %, it was heated at 60°C After 3 hours, a solution after the polymer was dissolved was obtained. 0.15 g of the above-mentioned dispersion liquid containing semiconductor fine particles and a solvent, and 0.913 g of the solution obtained by dissolving the polymer 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 into a size of 1 cm x 1 cm.

(Measurement of semiconductor fine particles)

The concentrations of the semiconductor fine particles in the compositions obtained in Examples and Comparative Examples were obtained by redispersing the dispersions containing semiconductor fine particles and a solvent, respectively, and adding N,N-dimethylformamide to make the semiconductor fine particles After dissolution, it was measured using ICP-MS (ELAN DRCII, manufactured by Perkin Elmer) and ion chromatography.

(Quantum Yield Measurement)

The quantum yields of the compositions obtained in Examples 1 to 14 and Comparative Example 1 were measured using an absolute PL quantum yield measuring apparatus (manufactured by Hamamatsu Photonics, trade name C9920-02, excitation light 450 nm, room temperature, atmosphere).

In Table 1 below, the constitutions and quantum yields (%) of the compositions of Examples 1 to 14 and Comparative Example 1 are described. In Table 1, the organic compound having a sulfhydryl group/Pb represents a molar ratio obtained by dividing the amount of the organic compound having a sulfhydryl group by the amount of Pb.

Figure 3 shows the results of Examples 1 to 4

From the above results, it was confirmed that the compositions of Examples 1 to 14 to which the present invention was applied were compared with the composition of Comparative Example 4 to which the present invention was not applied, and had excellent quantum yields.

[Reference Example 1]

The compositions described in Examples 1 to 14 are placed in a glass tube, etc. and sealed, and then placed between the blue light-emitting diodes of the light source and the light guide plate to produce blue light-converting blue light-emitting diodes. Backlight of green light or red light.

[Reference Example 2]

The composition described in Examples 1 to 14 can be thinned to obtain a resin composition, and the film sandwiched and sealed with 2 barrier films is placed on a light guide plate to manufacture a backlight, which will be placed on a light guide plate. The blue light emitting diode on the end face (side surface) of the light guide plate converts the blue light irradiated on the sheet to green light or red light through the light guide plate.

[Reference Example 3]

The compositions described in Examples 1 to 14 were placed near the light-emitting portion of the blue light-emitting diode to manufacture a backlight that converts irradiated blue light into green light or red light.

[Reference Example 4]

After mixing the compositions described in Examples 1 to 14 with a resist, a wavelength conversion material can be obtained by removing the solvent. The obtained wavelength conversion material is disposed between the blue light-emitting diode of the light source and the light guide plate, or the back-end of the OLED of the light source, to convert the blue light of the light source into green light or red light.

[Reference Example 5]

The compositions described in Examples 1 to 14 were mixed with conductive particles such as ZnS to form a film, an n-type transport layer was layered on one surface, and a p-type transport layer was layered on the other surface to obtain an LED. By flowing a current, the holes of the p-type semiconductor and the electrons of the n-type semiconductor can destroy the electric charges in the semiconductor fine particles of the junction surface, so that they emit light.

[Reference Example 6]

On the surface of a fluorine-doped tin oxide (FTO) substrate, a dense layer of titanium oxide was deposited, a porous alumina layer was deposited thereon, the compositions described in Examples 1 to 14 were deposited thereon, and the solvent was removed. , from which 2,2',7,7'-4-(N,N'-di-p-methoxyphenylamine)-9,9'-spirobis(spiro-OMeTAD), etc. On the hole transport layer, a silver (Ag) layer is laminated thereon to form a solar cell.

[Reference Example 7]

After mixing the compositions described in Examples 1 to 14 with the resin, remove the solvent and shape to obtain a resin composition containing the composition related to the present invention, which is placed in the latter stage of the blue light-emitting diode, and is fabricated from blue light emitting diodes. The light emitting diode illuminates the above-mentioned resin molded body with blue light converted into green light or red light, and a laser diode illumination for emitting white light.

[Industrial use possibility]

According to the present invention, a composition having a high quantum yield, a film composed of the composition, a laminate structure containing the composition, and a display using the composition can be provided.

Therefore, the composition of the present invention, a film composed of the composition, a laminated structure containing the composition, and a display using the composition can be suitably used for light-emitting applications.

1a‧‧‧The first laminated structure

10‧‧‧Film

20‧‧‧First substrate

21‧‧‧Second board

22‧‧‧Sealing layer

Claims (11)

A composition with luminescence, which contains (1), (2) and (3), and has luminescence; (1) semiconductor fine particles, (2) an organic compound having a hydrogen thiol group represented by the general formula (A5). Compound, R ¹⁴ -SH. . . (A5) In formula (A5), R ¹⁴ represents an optionally substituted alkyl group or an optionally substituted cycloalkyl group, and (3) at least one selected from the group consisting of a polymerizable compound and a polymer The content of (1) is 0.0001 mass % or more, and the total content of (1) and (2) is 0.0002 mass % or more with respect to the total mass of the aforementioned composition. The composition according to claim 1, wherein (1) is a fine particle of a perovskite compound having A, B and X as constituents; A is in the perovskite crystal structure and is located at B is the component of each vertex of the hexahedron with B as the center, and is a monovalent cation; X represents the component located at each vertex of the octahedron with B as the center in the perovskite crystal structure, and is selected from halogen One or more anions of the group consisting of compound ions and thiocyanate ions; B is in the perovskite crystal structure, and is located between the hexahedron where A is arranged at the vertex and the octahedron where X is arranged at the vertex. The central component, and is a metal ion. According to the composition described in item 1 or 2 of the scope of the application, relative to the group The total mass of the finished product, the content of (1) is 0.0001 to 50 mass %, and the total content of (1) and (2) is 0.0002 to 60 mass %. The composition as described in item 1 or 2 of the claimed scope further comprises (4) at least one selected from the group consisting of ammonia, amine, carboxylic acid, and salts or ions of these. A composition comprising (1), (2) and (3'), and the total content of (1), (2) and (3') is 90% by mass relative to the total mass of the composition The above; (1) semiconductor fine particles, (2) the organic compound having a hydrogen thiol group represented by the general formula (A5), R ¹⁴ -SH. . . (A5) In formula (A5), R ¹⁴ represents an alkyl group which may have a substituent group or a cycloalkyl group which may have a substituent group, (3') polymer; with respect to the total volume of the aforementioned composition, (1) The content is 0.01 g/L or more, and the total content of (1) and (2) is 0.02 g/L or more. For the composition described in item 5 of the scope of the application, relative to the total volume of the aforementioned composition, the content of (1) is 0.01 to 100 g/L, and the total content of (1) and (2) is 0.02 to 1000 g/L . The composition described in claim 5 or 6 of the claimed scope further comprises (4) at least one selected from the group consisting of ammonia, amine and carboxylic acid, and their salts or ions. A film, which is composed of the composition described in any one of items 5 to 7 of the patent application scope. A laminated structure having a plurality of layers, and at least one layer is composed of the composition described in any one of claims 5 to 7 of the scope of application. A light-emitting device comprising the laminated structure described in claim 9 of the scope of the application. A display is provided with the laminated structure described in claim 9 of the scope of application.

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