TWI746745B - Composition, film, laminated structure, light emitting device, and display - Google Patents

Abstract

The present invention relates to a compound comprising (1) and (2), further comprising at least one of (3) and (4), and having luminescent properties, wherein (1) is semiconductor fine particles, (2) is an organic compound having an ionic group other than the group represented by -NH₃ ⁺ or -COO^-, (3) is a solvent, and (4) 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 a composition, a film, a laminated structure, a light-emitting device, and a display.

This application claims priority based on Japanese Patent Application No. 2016-250170 filed on December 22, 2016 in Japan, and the content is used here.

In recent years, interest in the luminescence characteristics of semiconductor materials has continued to increase.

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

[Prior Technical 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 Non-Patent Document 1 is used as a luminescent material, it is required to further improve the quantum yield.

The present invention was made in view of the above-mentioned problems, and its object is to provide a composition, a film, a multilayer structure, a light-emitting device, and a display that contain semiconductor microparticles and have a high quantum yield.

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

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

[1] A luminescent composition containing (1) and (2), and further containing at least one of (3) and (4); (1) semiconductor particles, (2) having -NH ₃ ⁺ the base shown and -COO ^- an organic compound other than the group represented by an ionic group, (3) a solvent, (4) selected from the group consisting of a polymerizable compound and a polymer formed by at least one of the group.

[2] The composition according to the aforementioned [1], wherein the aforementioned (1) is a fine particle of a perovskite compound having A, B, and X as constituent components; A is in a perovskite-type crystal structure, The component located at each vertex of the hexahedron centered on B, and is a monovalent cation; X represents the component located at each vertex of the octahedron centered on B in the perovskite crystal structure, select One or more anions grouped by free halide ions and thiocyanate ions; B is in the perovskite crystal structure, located in the hexahedron where A is placed at the apex and X is placed at the eighth side at the apex The component in the center of the body, and is a metal ion.

[3] The composition as described in the aforementioned [1] or [2], which further contains (5) at least 1 selected from the group consisting of ammonia, amines, carboxylic acids, and these salts or ions kind.

[4] A composition containing the composition of (1), (2) and (4'), and the total content of (1), (2) and (4') is relative to the total mass of the aforementioned composition 90% by mass or more; (1) semiconductor microparticles, (2) organic compounds having ionic groups other than the group _{represented by -NH 3} ^{+ and} the group represented by -COO ^{-, (4') polymer.}

[5] The composition as described in [4] above, which further contains (5) at least one selected from the group consisting of ammonia, amines, carboxylic acids, and these salts or ions.

[6] A film composed of the composition described in [4] or [5] above.

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

[8] A light-emitting device comprising the multilayer structure described in [7] above.

[9] A display comprising the multilayer structure described in the item [7] above.

According to the present invention, it is possible to provide a composition, a film, a multilayer structure, a light-emitting device, and a display containing semiconductor microparticles with high quantum yield.

1a‧‧‧The first multi-layer structure

1b‧‧‧Second layered structure

2‧‧‧Light-emitting device

3‧‧‧Display

10‧‧‧membrane

20‧‧‧The first substrate

21‧‧‧Second substrate

22‧‧‧Sealing layer

30‧‧‧Light source

40‧‧‧LCD Panel

50‧‧‧Silver slices

60‧‧‧Light guide plate

Figure 1 shows a cross-sectional view of one embodiment of the laminated structure according to the present invention.

Figure 2 shows a cross-sectional view of an embodiment of the display related to the present invention.

Figure 3 is a graph showing the quantum yield results of the composition related to the present invention obtained in the examples.

Figure 4 is a graph showing the quantum yield results of the composition related to the present invention obtained in the examples.

Hereinafter, embodiments are shown to describe the present invention in detail.

<Composition>

The composition of the present invention has luminescence. The so-called "luminescence" refers to the property of emitting light. The luminescence is preferably the property of luminescence by electron excitation, and more preferably the property of luminescence by the excitation of electrons generated by 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) and (2), and further contains at least one of (3) and (4).

(1) Semiconductor fine particles, (2) Organic compounds having groups represented by _{-NH 3} ^{+ and ionic groups other than groups represented by -COO -} , (3) Solvents, (4) selected from polymerizable compounds and polymerization At least one of the group of things.

(2) The organic compound is a group that does not have any of the group represented by _{-NH 3} ^{+ and the group represented by -COO -} .

The aforementioned composition system may further contain (5) at least one selected from the group consisting of ammonia, amine, carboxylic acid, and these salts or ions.

In addition, the aforementioned composition system may have components other than the above-mentioned (1) to (5).

Other component systems include, for example, some impurities, compounds having an amorphous structure composed of elemental components constituting semiconductor fine particles, and polymerization initiators.

The content of other components is preferably 10% by mass or less with respect to the total mass of the composition, more preferably 5% by mass or less, and most preferably 1% by mass or less.

As a result of intensive research, the inventors found that the following (1), (2), (3) and (4) contain (1) and (2), and further contain at least one of (3) and (4) The quantum yield can be improved in the composition of those; (1) semiconductor microparticles, (2) _{organic compounds with groups shown by -NH 3} ⁺ and ionic groups other than groups shown by ^{-COO -, (3) solvents} , And (4) one or more selected from the group consisting of polymerizable compounds and polymers.

Xian believes that this is because the organic compound of (2) can prevent the electrons trapped by the surface defects of the semiconductor particles of (1) from losing their activity. Since the electrons are excited, the quantum yield can be improved.

In the composition of this embodiment, the total content of at least one of (1) and (2), and (3) and (4) may be 90% by mass or more relative to the total mass of the aforementioned composition, and may be 95%. The mass% or more may be 99 mass% or more, or it may be 100 mass %.

The composition of the present invention may contain (1), (2) and (4'), and the total content of (1), (2) and (4') is 90% by mass or more relative to the total mass of the aforementioned composition The composition.

(1) Semiconductor fine particles, (2) An organic compound having a group represented by _{-NH 3} ⁺ and an ionic group other than the group represented by ^{-COO -, (4') polymer.}

In the composition of this embodiment, the total content of (1), (2) and (4') relative to the total mass of the aforementioned composition may be 95% by mass or more, or 99% by mass or more, or 100% by mass.

The composition system may further contain (5) at least one selected from the group consisting of ammonia, amine, carboxylic acid, and these salts or ions. Examples of components other than (1), (2), (4'), and (5) include the same components as the other components described above.

In the composition of the present embodiment containing any one or both of (1), (2), and (3) and (4), the content of (1) is not particularly limited relative to the total mass of the composition However, from the standpoint of easily condensing the semiconductor fine particles and the standpoint of preventing concentration extinction, 50% by mass or less is preferable, 1% by mass or less is more preferable, and 0.1% by mass or less is even more preferable. From the viewpoint of obtaining a good quantum yield, 0.0001% by mass or more is preferable, 0.0005% by mass or more is more preferable, and 0.001% by mass or more is even more preferable.

The above upper limit and lower limit can be combined arbitrarily.

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

Relative to the total mass of the composition, the content of (1) is preferably 0.0001 to 1% by mass, more preferably 0.0005 to 1% by mass, and still more preferably 0.001 to 0.1% by mass.

The range related to the formulation 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 difficult to produce and the luminescence is also exhibited well.

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

In the composition of the present embodiment containing any one or both of (1), (2), and (3) and (4), relative to the total mass of the composition, the difference between (1) and (2) The total content is not particularly limited, but from the standpoint of easily condensing semiconductor fine particles and preventing concentration extinction, 60% by mass or less is preferable, 10% by mass or less is more preferable, and 2% by mass or less is more preferable. More preferably, 0.2% by mass or less is particularly preferable. From the viewpoint of obtaining good quantum yield, 0.0002% by mass or more is more preferable, 0.002% by mass or more is more preferable, and 0.005% by mass or more is still more preferable. good.

The above upper limit and lower limit can be combined arbitrarily.

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

Relative 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 still more preferably 0.005 to 0.2% by mass.

The range related to the blending ratio of (1) and (2) is a composition within the above-mentioned range, and it is preferable that the aggregation of the semiconductor fine particles of (1) is difficult to produce, and the luminescence is also exhibited well.

In addition, the above (2) organic compound having a group represented by _{-NH 3} ^{+ and an ionic group other than the group represented by -COO-is} selected from the group consisting of ammonia, amines, carboxylic acids, and the like in (5) above A compound other than at least one compound in the group of salts or ions.

In the composition of this embodiment containing (1), (2) and (4'), the content of (1) relative to the total volume of the composition is not particularly limited, but from the viewpoint of easy condensation of semiconductor fine particles , And to prevent concentration extinction, 100g/L or less is preferable, 10g/L or less is more preferable, 5g/L or less is more preferable, and from the viewpoint of obtaining good quantum yield, 0.01 g/L or more is preferable, 0.1 g/L or more is more preferable, and 0.5 g/L or more is even more preferable.

The above upper limit and lower limit can be combined arbitrarily.

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 formulation of (1) is a composition within the above-mentioned range, and it is preferable in terms of good luminescence performance.

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

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

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

When the composition is a powder, the total volume of the composition can be calculated by measuring the bulk density in accordance with JIS R 93-1-2-3: 1999, and dividing the weight of the composition used for the measurement by the aforementioned bulk density.

In the composition of this embodiment containing (1), (2) and (4'), the total content of (1) and (2) is not particularly limited relative to the total volume of the composition, but it is easy to use From the viewpoint of condensation of semiconductor particles and the viewpoint of preventing concentration extinction, 1000g/L or less is more preferable, 500g/L or less is more preferable, and 300g/L or less is more preferable. In addition, good quantum yield can be obtained. From the viewpoint of rate, 0.02 g/L or more is preferable, 0.2 g/L or more is more preferable, and 0.6 g/L or more is still more preferable.

The above upper limit and lower limit can be combined arbitrarily.

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, and even more preferably 0.6 to 300 g/L.

The range related to the blending ratio of (1) and (2) is a composition within the above-mentioned range, and it is preferable in terms of good luminescence performance.

Hereinafter, embodiments are shown to explain the composition in the present invention.

(1) Semiconductor particles

The composition related to the present invention contains (1) semiconductor fine particles, and (1) semiconductor fine particles are preferably dispersed. Examples of the dispersant include (3) solvents, (4) at least one selected from the group consisting of polymerizable compounds and polymers, and (4') polymers.

In this specification, "dispersed" refers to a state where semiconductor particles are floating or suspended in the dispersant.

The semiconductor particles can include, for example, the crystal particles of group II-VI compound semiconductors, the crystal particles of group II-V compound semiconductors, the crystal particles of group III-V compound semiconductors, and the crystals of group III-IV compound semiconductors. The fine particles of the crystals of the group III-VI compound semiconductors, the crystal particles of the group IV-VI compound semiconductors, the crystal particles of the transition metal-p-block compound semiconductor, and the fine particles of the perovskite compound.

From the viewpoint of obtaining a good quantum yield, semiconductor particles are preferably crystalline particles of semiconductors containing cadmium, crystalline particles of semiconductors containing indium, and particles of perovskite compounds. The particle size control is not so strict. For the point of easily obtaining the luminescence peak with the half-height width, the fine particles of the perovskite compound are more preferable.

At least a part of these semiconductor fine particles may be coated with (2) an organic compound having an ionic group containing at least one type of ionic group other than the group _{represented by -NH 3} ^{+ and} the group represented by -COO ^-.

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 more preferably 3 nm or more Preferably, from the viewpoint that it is difficult to settle the semiconductor fine particles related to the present invention, 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 upper limit and lower limit can be combined arbitrarily.

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

In this specification, the average particle size 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.) and a scanning electron microscope (hereinafter, also referred to as SEM.) . Specifically, by observing the maximum Feret diameter of 20 semiconductor microparticles contained in the aforementioned composition by TEM or SEM, and calculating the average maximum Feret diameter of the average value thereof, the aforementioned average particle diameter can be obtained. The "maximum Feret diameter" in this specification means the maximum distance between two parallel straight lines sandwiching semiconductor 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 more preferably 5 nm or more. Preferably, from the viewpoint that it is difficult to settle the semiconductor fine particles related to the present invention, 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 this embodiment is that the median diameter (D50) of the particle size distribution of the semiconductor fine particles contained in the composition is preferably 3nm to 5μm, more preferably 4nm to 500nm, and more preferably 5nm to 100nm. good.

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

(II-VI group compound semiconductor crystal particles)

Group II-VI group compound semiconductors refer to elements containing Group 2 or Group 12 and Group 16 elements of the Periodic Table.

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

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

The binary system II-VI group compound semiconductor system containing elements selected from the group 2 of the periodic table (the first element) and the group 16 elements (the second element) of the periodic table can be, for example, MgS, MgSe, MgTe, CaS, CaSe, CaTe, SrS, SrSe, SrTe, BaS, BaSe, or BaTe.

It can be a group II-VI group compound semiconductor containing a group 2 element selected from the periodic table (the first element) and a group 16 element selected from the periodic table (the second element) containing a group 2 element selected from the periodic table ( The first element) 1 type, and a ternary system II-VI group compound semiconductor of 2 types selected from the 16th group element (the second element) of the periodic table, or may be a compound semiconductor containing a 2nd group element selected from the periodic table (the first Element) 2 types, and a ternary II-VI group compound semiconductor of 1 type selected from the 16th group element (second element) of the periodic table, which may contain a group 2 element (the first element) 2 selected from the periodic table Types, and two types of quaternary system II-VI group compound semiconductors selected from the 16th group element (second element) of the periodic table.

The binary system II-VI group compound semiconductor system containing the 12th group element selected from the periodic table (the first element) and the 16th group element selected from the periodic table (the second element) can include, for example, ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, HgS, HgSe, or HgTe.

It can be a group II-VI compound semiconductor containing an element selected from the 12th group of the periodic table (the first element) and an element selected from the 16th group (the 2nd element) of the periodic table, and it can be a compound semiconductor containing 12 Group element (1st element) 1 type, and ternary system II-VI group compound semiconductor of 2 types selected from 16 group element (2nd element) of the periodic table, or may contain 12 group elements selected from the periodic table (The first element) 2 types, and a ternary system II-VI group compound semiconductor of 1 type selected from the 16th group element of the periodic table (the 2nd element), or may be a compound semiconductor containing a 12th group element selected from the periodic table (the second element) 1 element) 2 types, and 2 types of quaternary group II-VI group compound semiconductors selected from group 16 elements (second element) of the periodic table.

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

(II-Group V compound semiconductor crystal particles)

The group II-V group compound semiconductor system contains elements of group 12 and group 15 of the periodic table.

The binary system II-V group compound semiconductor system containing the element from the 12th group of the periodic table (the first element) and the 15th element (the second element) from the periodic table can 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 .

Group II-V compound semiconductors containing elements from group 12 of the periodic table (the first element) and elements from group 15 (element 2) of the periodic table, which may contain elements from group 12 of the periodic table (The first element) 1 type, and 2 types of ternary system II-V group element selected from the 15th group of the periodic table (the 2nd element), or may be a compound semiconductor containing the 12th group element selected from the periodic table (the second element) 1 element) 2 types, and 1 type of ternary system II-V group compound semiconductors selected from the 15th group of the periodic table (the 2nd element), or may be a compound semiconductor containing the 12th group selected from the periodic table (the 1st element) ) 2 types, and 2 types of quaternary system II-V group compound semiconductors selected from group 15 elements (second element) of the periodic table. The group II-V group compound semiconductor system may contain elements other than groups 12 and 15 of the periodic table as doping elements.

(Crystalline particles of group III-V compound semiconductors)

The group III-V compound semiconductor system contains elements from group 13 of the periodic table and elements from group 15 of the periodic table. The binary system group III-V group compound semiconductor system containing an element selected from the group 13 of the periodic table (the first element) and an element selected from the group 15 (the second element) of the periodic table can 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 from group 13 of the periodic table (the first element) and elements from group 15 (element 2) of the periodic table, which may contain elements from group 13 of the periodic table (The first element) 1 type, and 2 types of ternary system III-V compound semiconductors selected from the 15th group element of the periodic table (the 2nd element), or may be a compound semiconductor containing a 13th group element selected from the periodic table (the second element) 1 element) 2 types, and 1 type of ternary system III-V group compound semiconductors selected from the 15th group of the periodic table (the 2nd element), or may contain 13 groups selected from the periodic table (the 1st element) ) 2 types and 2 types of quaternary group III-V group compound semiconductors selected from group 15 elements (second element) of the periodic table.

Group III-V compound semiconductors may contain elements other than Group 13 and Group 15 of the periodic table as doping elements.

(Crystalline particles of group III-IV compound semiconductors)

Group III-IV compound semiconductors contain elements from group 13 of the periodic table and elements from group 14 of the periodic table. The two-membered group III-IV compound semiconductor system containing an element selected from the group 13 of the periodic table (the first element) and an element selected from the group 14 (the second element) of the periodic table can be, for example, B ₄ C ₃ , Al ₄ C ₃ , Ga ₄ C ₃ .

Group III-IV compound semiconductors containing elements selected from the group 13 of the periodic table (the first element) and group 14 elements (the second element) of the periodic table, which may contain elements from the group 13 of the periodic table (The first element) 1 type and 2 types of ternary group III-IV compound semiconductors selected from the 14th group of the periodic table (the 2nd element), or may be a compound semiconductor containing group 13 elements selected from the periodic table (the No. 1 element) 2 types, and 1 type of ternary group III-IV group compound semiconductors selected from the 14th group of the periodic table (the 2nd element), or may be a group 13 element selected from the periodic table (the 1st element) ) 2 types, and 2 types of quaternary group III-IV group compound semiconductors selected from the group 14 elements (the second element) of 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.

(Crystal particles of group III-VI compound semiconductors)

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

A binary group III-VI group compound semiconductor containing an element selected from the group 13 of the periodic table (the first element) and an element selected from the group 16 (the 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 from group 13 of the periodic table (the first element) and elements from group 16 (element 2) of the periodic table, which may contain elements from group 13 of the periodic table (The first element) 1 type and 2 types of ternary system III-VI group element selected from the 16th group of the periodic table (the 2nd element), or may be a compound semiconductor containing group 13 elements selected from the periodic table (the second element) 1 element) 2 types, and 1 type of ternary system III-VI group compound semiconductors selected from the 16th group element of the periodic table (the second element), or may be a group 13 element selected from the periodic table (the 1st element) ) 2 types, and 2 types of quaternary group III-VI group compound semiconductors selected from the group 16 element (the second element) of the periodic table.

Group III-VI compound semiconductors may contain elements other than Group 13 and Group 16 of the periodic table as doping elements.

(Crystal particles of group IV-VI compound semiconductors)

The group IV-VI group compound semiconductor system contains elements selected from the group 14 of the periodic table, and elements selected from the group 16 of the periodic table. A binary group IV-VI group compound semiconductor containing an element selected from the 14th group of the periodic table (the first element) and an element selected from the 16th group (the second element) of the periodic table, such as PbS, PbSe, PbTe , SnS, SnSe, or SnTe.

Group IV-VI compound semiconductors containing group 14 elements selected from the periodic table (first element) and group 16 elements selected from the periodic table (second element), which may contain group 14 elements selected from the periodic table (The first element) 1 type and 2 types of ternary system IV-VI group element selected from the 16th group of the periodic table (the 2nd element), or may be a compound semiconductor containing group 14 elements selected from the periodic table (the second element) 1 element) 2 types, and 1 type of ternary system IV-VI group compound semiconductors selected from the 16th group of the periodic table (the second element), which may contain 14 group elements (the 1st element) selected from the periodic table Two types, and two types of quaternary system IV-VI group compound semiconductors selected from the group 16 element (second element) of the periodic table.

The group IV-VI group compound semiconductor system may contain elements other than groups 14 and 16 of the periodic table as doping elements.

(Transition metal-p-block compound semiconductor crystal particles)

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

A binary transition metal-p-block compound semiconductor containing an element selected from the transition metal element of the periodic table (the first element) and an element selected from the p-block element (the second element) of the periodic table, Examples include NiS and CrS.

The transition metal-p-block compound semiconductor selected from the element of the transition metal element of the periodic table (the first element) and the element selected from the p-block element (the second element) of the periodic table, which may contain optional One type of element (first element) from the periodic table of transition metal elements and two types of element (second element) selected from p-block elements are ternary transition metal-p-block compound semiconductors, which may contain Two types of elements selected from the transition metal elements of the periodic table (first element), and one type of ternary transition metal-p-block compounds selected from the element of p-block elements of the periodic table (second element) Semiconductor, or may be a quaternary transition metal containing two types of elements selected from the transition metal elements of the periodic table (first element) and two types of elements selected from the p-block element (second element) of the periodic table -p-block compound semiconductor.

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

Specific examples of the above-mentioned ternary and quaternary semiconductors include, for example, ZnCdS, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHg, Se, CdHgTe HgZnS, HgZnSe, HgZnTe, ZnCdSSe, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, HgZnSTe, GaNP, GaNAs, GaPAs, AlNPs, AlInGas, AlNPs, AlInGas, AlNP, GaPANP, GaInNP, GaInNAs, GaInPAs, InAlNP, InAlNAs, CuInS ₂ , or InAlPAs, etc.

(Perovskite compound)

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

The perovskite compound is a compound having a perovskite-type crystal structure having A, B, and X as constituent components.

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

X represents a component located at each vertex of an octahedron centered at B in the aforementioned perovskite crystal structure, and is selected from 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 with the A position at the apex and the octahedron with the X at the apex in the aforementioned perovskite crystal structure, and is a metal ion.

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

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

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

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

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

In the above three-dimensional structure, there is a three-dimensional network in which the vertices shown by _{BX 6 with B as the center and X as the vertices share an octahedron.}

In the above two-dimensional structure, by sharing the four vertices X of the same plane with the eight faces _{of BX 6} with B as the center and the vertex X, forming a two-dimensionally connected layer _{composed of BX 6} And a structure made up of alternate layers of A.

B is a metal cation with octahedral coordination of X.

A is located at each vertex of the hexahedron centered on B.

In this manual, the ilmenite crystal structure can be confirmed by X-ray diffraction pattern.

In the case of the aforementioned compound with a three-dimensional structure of perovskite crystal structure, in the X-ray diffraction pattern, usually, the peak derived from (hkl)=(001) can be confirmed at the position of 2θ=12 to 18° , Or confirm the peak derived from (hkl)=(100) at the position of 2θ=18-25°. 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 aforementioned compound with a two-dimensional structure of perovskite crystal structure, in the X-ray diffraction pattern, the peak derived from (hkl)=(002) can usually be confirmed at the position of 2θ=1 to 10°. It is better to confirm the peak derived from (hkl)=(002) 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 an anion selected from one or more types of halide ions and thiocyanate ions. ]

〔A〕

In the perovskite compound related 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. Examples of monovalent cations include cesium ion, organic ammonium ion, or amidine ion. In perovskite compounds, when A is cesium ion, organic ammonium ion with carbon number of 3 or less, or amidine ion with carbon number of 3 or less, in general, perovskite compound has ABX _(3+δ) The three-dimensional structure.

Among the compounds, cesium ion or organic ammonium ion is preferred for A system.

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, and may have an amino group as a substituent.

The ^{number of carbon atoms of the alkyl group represented by R 6} to R ⁹ is usually 1 to 20, preferably 1 to 4, and more preferably 1 to 3.

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

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

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

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

The total number of carbon atoms contained in the alkyl group and cycloalkyl group represented by R ⁶ to R ^{9 is preferably 1 to 4, and one of R 6} to R ⁹ is an alkane with 1 to 3 carbon atoms. It is more preferable that three 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, secondary-butyl, tertiary-butyl, n-pentyl, isoamyl 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 Base, 3,3-dimethylpentyl, 3-ethylpentyl, 2,2,3-trimethylbutyl, n-octyl, isooctyl, 2-ethylhexyl, nonyl, decyl , Undecyl, twelve-carbon, thirteen-carbon, fourteen-carbon, fifteen-carbon, sixteen-carbon, seventeen-carbon, eighteen-carbon, nineteen-carbon, twenty-carbon .

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 ion shown in A is CH ₃ NH ₃ ⁺ (also called methyl ammonium ion.), C ₂ H ₅ NH ₃ ⁺ (also called ethyl ammonium ion.) or C ₃ H ₇ NH ₃ ⁺ (Also called propylammonium ion.) is preferred, CH ₃ NH ₃ ⁺ or C ₂ H ₅ NH ₃ ⁺ is more preferred, and CH ₃ NH ₃ ⁺ is most preferred.

Examples of the amidine ion represented by A include 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 amino 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, and more preferably 1 to 3.

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

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

Specific examples of the cycloalkyl group of R ¹⁰ to R ^{13 include the cycloalkyl groups exemplified in R 6} to R ⁹ .

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

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

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

[B]

In the perovskite compound, B is a component located at the center of a hexahedron with A at the vertex and an octahedron with X at the vertex in the perovskite crystal structure, and represents a metal ion. The metal ion of the B component includes one or more types of ions selected from the group consisting of monovalent metal ions, divalent metal ions, and trivalent metal ions. B preferably contains a divalent metal ion, and more preferably contains one or more metal ions selected from the group consisting of lead or tin.

〔X〕

X series represents one or more anions selected from the group consisting of halide ions and thiocyanate ions. The X series may be one or more anions selected from the group consisting of chloride ion, bromide ion, fluoride ion, iodide ion, and thiocyanate ion.

The X system can be appropriately selected according to the desired emission wavelength, but for example, X may contain bromide ions.

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

Regarding the perovskite compound and the perovskite type crystal structure of the three-dimensional structure shown by _{ABX (3+δ) , specific examples 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) 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) Cl _y (0<y<3), CH ₃ NH ₃ PbBr _(3-y) Cl _y (0 <y<3), CH ₃ NH ₃ Pb _(1-a) Zn _a Br _(3+δ) (0<a≦0.7, 0≦δ≦0.7), CH ₃ NH ₃ Pb _(1-a) Al _a Br _(3+δ) (0<a≦0.7, 0≦δ≦0.7), CH ₃ NH ₃ Pb _(1-a) Co _a Br _(3+δ) (0<a≦0.7, 0≦δ≦0.7) ), CH ₃ NH ₃ Pb _(1-a) Mn _a Br _(3+δ) (0<a≦0.7, 0≦δ≦0.7), CH ₃ NH ₃ Pb _(1-a) Mg _a Br _{(3+ δ)} (0<a≦0.7, 0≦δ≦0.7), CsPb _(1-a) Zn _a Br _(3+δ) (0<a≦0.7, 0≦δ≦0.7), CsPb _(1-a) Al _a Br _(3+δ) (0<a≦0.7, 0≦δ≦0.7), CsPb _(1-a) Co _a Br _(3+δ) (0<a≦0.7, 0≦δ≦0.7), CsPb _(1-a) Mn _a Br _(3+δ) (0<a≦0.7, 0≦δ≦0.7), CsPb _(1-a) Mg _a Br _(3+δ) (0<a≦0.7, 0 ≦δ≦0.7), CH ₃ NH ₃ Pb _(1-a) Zn _a Br _(3+δ-y) I _y (0<a≦0.7, 0≦δ≦0.7, 0<y<3), CH ₃ NH ₃ Pb _(1-a) Al _a Br _(3+δ-y) I _y (0<a≦0.7, 0≦δ≦0.7, 0<y<3), CH ₃ NH ₃ Pb _(1-a) Co _a Br _(3+δ-y) I _y (0<a≦0.7, 0≦δ≦0.7, 0<y<3), CH ₃ NH ₃ Pb _(1-a) Mn _a Br _(3+δ-y) I _y (0 <a≦0.7, 0≦δ≦0.7, 0<y<3), CH ₃ NH ₃ Pb _(1-a) Mg _a Br _{(3+δ- y)} I _y (0<a≦0.7, 0≦δ≦0.7, 0<y<3), CH ₃ NH ₃ Pb _(1-a) Zn _a Br _(3+δ-y) Cl _y (0<a ≦0.7, 0≦δ≦0.7, 0<y<3), CH ₃ NH ₃ Pb _(1-a) Al _a Br _(3+δ-y) Cl _y (0<a≦0.7, 0≦δ≦0.7 , 0<y<3), CH ₃ NH ₃ Pb _(1-a) Co _a Br _(3+δ-y) Cl _y (0<a≦0.7, 0≦δ≦0.7, 0<y<3), CH 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) Cl _y (0<a≦0.7, 0≦δ≦0.7, 0<y<3), etc. are preferable.

Regarding the perovskite compound having a perovskite-type crystal structure of the two-dimensional structure shown 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) Cl _y (0<y<4), (C ₄ H ₉ NH ₃ ) ₂ PbBr _(4-y) I _y (0 <y<4), (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Zn _a Br _(4+δ) (0<a≦0.7), (C ₄ H ₉ NH ₃ ) ₂ Pb _{(1- a)} Mg _a Br _(4+δ) (0<a≦0.7, 0≦δ≦0.7), (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Co _a Br _(4+δ) (0< a≦0.7, 0≦δ≦0.7), (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Mn _a Br _(4+δ) (0<a≦0.7, 0≦δ≦0.7), (C ₇ H ₁₅ NH ₃ ) ₂ Pb _(1-a) Zn _a 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) Cl _y (0<a≦0.7, 0≦δ≦0.7, 0<y<4), (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Mg _a Br _{( 4+δ-y)} Cl _y (0<a≦0.7, 0≦δ≦0.7, 0≦δ≦0.7, 0<y<4), (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Co _a Br _(4+δ-y) Cl _y (0<a≦0.7, 0≦δ≦0.7, 0<y<4), (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Mn _a Br _(4+δ-y) Cl _y (0<a≦0.7, 0≦δ≦0.7, 0<y<4), etc. are preferable.

≪Luminescence spectrum≫

Perovskite compound is a luminous body that can emit fluorescence in the visible wavelength region. When X is bromide ion, it is usually 480nm or more, preferably 500nm or more, more preferably 520nm or more, and usually 700nm or less, preferably The wavelength range below 600nm, more preferably below 580nm, can emit fluorescence with extremely large peaks of intensity.

The above upper limit and lower limit can be combined arbitrarily.

In another aspect of the present invention, when X in the perovskite compound is bromide ion, the fluorescence peak is usually 480 to 700 nm, preferably 500 to 600 nm, and more preferably 520 to 580 nm.

When X is an iodide ion, it is usually 520nm or more, preferably 530nm or more, more preferably 540nm or more, and usually 800nm or less, preferably 750nm or less, and more preferably 730nm or less. The wavelength range can emit intensity. The fluorescence of the largest peak.

The above upper limit and lower limit can be combined arbitrarily.

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

When X is chloride ion, it is usually 300nm or more, preferably 310nm or more, more preferably 330nm or more, and usually 600nm or less, preferably 580nm or less, more preferably 550nm or less. Fluorescence of the highest peak of intensity.

The above upper limit and lower limit can be combined arbitrarily.

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

(2) having a group represented by the ₃ ⁺ and -COO -NH ^- an organic compound other than an ionic group represented by the group

The aforementioned organic compound having an ionic group is an organic compound having an anionic group or a cationic group.

The organic compound having an ionic group is preferably an organic compound having a cationic group.

Here, the anionic group means a group having a negative charge, and the cationic group means a group having a positive charge.

The organic compound having an ionic group may be a compound having an anionic group represented by the following general formula (A5).

R ¹⁴ -Y‧‧‧(A5)

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

When R ¹⁴ is an alkyl group, it may be linear or branched. The number of carbon atoms of the alkyl group is usually 1-20, preferably 5-20, and more preferably 8-20.

When R ¹⁴ is a cycloalkyl group, the cycloalkyl system may have an alkyl group as a substituent. The number of carbon atoms is usually 3 to 30, preferably 3 to 20, and more preferably 3 to 11. The number of carbon atoms is the number of carbon atoms containing substituents.

Among these, R ¹⁴ is preferably an alkyl group.

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

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

In the general formula (A5), Y represents a line -COO ^- anionic group other than the group shown in FIG. The anionic group Y may be for example as shown in the group represented by -PO ₄ ^2-, -OSO ₃ ^- as shown in the group, -OSO ₃ ^- the group represented by are preferred.

Part or all of the organic compound having an anionic group represented by the general formula (A5) can be adsorbed on the surface of the semiconductor fine particles related to the present invention, and can also be dispersed in the composition.

The organic compound having an anionic group represented by the general formula (A5) can form a salt with a relative cation. The relative cation in the anionic group is not particularly limited, but examples include monovalents of ^{Na +} , K ⁺ , and Cs ⁺ ion.

The organic compound having an anionic group represented by the general formula (A5) and the salt having a relatively cation include, for example, alkyl sulfate, alkyl phosphate, alkyl sulfonate, etc., lauryl phosphoric acid, sodium lauryl phosphate , Oleyl phosphoric acid, sodium 1-hexane sulfonate, sodium 1-octane sulfonate, sodium 1-decane sulfonate, sodium 1-dodecane sulfonate, sodium hexadecyl sulfate, stearyl sulfuric acid Sodium, sodium lauryl sulfate, sodium myristyl sulfate, sodium laureth sulfate, and sodium lauryl sulfate are preferred, and sodium lauryl sulfate is more preferred.

The organic compound having an ionic group may be a compound having a cationic group represented by the following general formula (A6-1) or (A6-2).

In general formula (A6-1) and general formula (A6-2), R ¹⁵ represents an optionally substituted alkyl group or an optionally substituted cycloalkyl group, and R ¹⁶ to R ¹⁸ each independently represent hydrogen Atom, an alkyl group which may have a substituent, or a cycloalkyl group which may have a substituent.

The alkyl group represented by R ¹⁵ to R ¹⁸ may be linear or branched, and may have a substituent.

The alkyl group represented by R ¹⁵ to R ¹⁸ may have a cationic group as a substituent.

The ^{number of carbon atoms of the alkyl group represented by R 15} to R ¹⁸ is usually 1 to 20, preferably 5 to 20, and more preferably 8 to 20. The aforementioned number of carbon atoms is the number of carbon atoms containing a substituent.

The cycloalkyl system represented by R ¹⁵ to R ¹⁸ may have an alkyl group as a substituent, or may have a cationic group.

The ^{number of carbon atoms of the cycloalkyl group represented by R 15} to R ¹⁸ is usually 3 to 30, preferably 3 to 20, and more preferably 3 to 11. The aforementioned number of carbon atoms is the number of carbon atoms containing a substituent.

Preferably, R ¹⁶ to R ¹⁸ are each independently a hydrogen atom or the aforementioned alkyl group, more preferably at least one of ^{R 15} to R ¹⁸ is the aforementioned alkyl group, and at least two of ^{R 15} to R ^{18 are} The aforementioned alkyl group is more preferable. It is particularly preferable that one of R ¹⁵ to R ¹⁸ is an alkyl group having 8 to 20 carbon atoms, and three of R ¹⁵ to R ¹⁸ are an alkyl group having 1 to 5 carbon atoms.

Specific examples of the alkyl groups of R ¹⁵ to R ^{18 include the alkyl groups exemplified in R 6} to R ⁹ .

Specific examples of the cycloalkyl group of R ¹⁵ to R ^{18 include the cycloalkyl group exemplified in R 6} to R ⁹ .

In the general formula (A6-1), Z ⁺ system represents a cation. The cation that can obtain the structure of the general formula (A6-1) includes, for example, an ion of an element with 5 electrons existing in the outermost shell, and ^{the cation represented by Z +} includes, for example, P ^{+ and N +} .

When Z ⁺ is N ^{+ , at least one of R 16} to R ¹⁸ in the general formula (A6-1) represents an optionally substituted alkyl group or an optionally substituted cycloalkyl group. ^{Two or more of R 16} to R ¹⁸ in the general formula (A6-1) may be an alkyl group which may have a substituent or a cycloalkyl group which may have a substituent.

In the general formula (A6-2), Z ⁺ system represents a cation. The cation that can take the structure of the general formula (A6-2) may be, for example, an ion of an element with 6 electrons existing in the outermost shell, and ^{the cation represented by Z +} may be, for example, S ⁺ .

The compound having a cationic group represented by the following general formula (A6-1) or (A6-2) is preferably a compound having a cationic group represented by the general formula (A6-1) in which ^{Z +} is P ^+, And the compound having a cationic group represented by the general formula (A6-2) in which ^{Z +} is S ⁺ is more preferably a compound having a cationic group represented by the general formula (A6-1) in which ^{Z +} is P ^+.

Part or all of the organic compounds with cationic groups represented by the general formula (A6-1) and general formula (A6-2) can be adsorbed on the surface of the semiconductor microparticles related to the present invention, or on the composition Moderately dispersed.

Based organic compound having a cationic group may form a salt with a cation opposite, the opposite is not particularly limited in the cationic anionic groups, but for example, such as ^{Br -, Cl -, I -} , F - ions of the halogen compounds.

The organic compound having a cationic group represented by the general formula (A6-1) and the relatively anionic salt include, for example, phosphonium salt, etc. The phosphonium salt is preferably tetraphenylphosphonium chloride, tributylhexadecane chloride Carbonyl phosphonium, tetrabutyl phosphonium chloride, tetraethyl phosphonium chloride, tetra-n-octyl phosphonium chloride, tetraphenyl phosphonium bromide, tributyl hexadecyl phosphonium bromide, tetrabutyl phosphonium bromide Phosphonium, tetraethyl phosphonium bromide, tetra-n-octyl phosphonium bromide, tributyl dodecyl phosphonium bromide, tributyl-n-octyl phosphonium bromide, tetraphenyl phosphonium iodide, triiodide Butyl hexadecyl phosphonium, tetrabutyl phosphonium iodide, tetraethyl phosphonium iodide, and tetra-n-octyl phosphonium iodide are preferred, and tributyl hexadecyl phosphonium bromide is more preferred.

Examples of the organic compound having a cationic group represented by the general formula (A6-2) and the relatively anionic salt include sulfonium salt. Examples of the sulfonium salt series include tributyl alumium iodide and tributyl alumium bromide. , Trimethyl alumium hydroxide, etc.

(2) The organic compound is preferably selected from the compound having an anionic group represented by the aforementioned general formula (A5), the compound having a cationic group represented by the aforementioned general formula (A6-1), and the aforementioned general formula ( At least one of the group of compounds having a cationic group shown in A6-2).

Regarding another aspect of the present invention, (2) organic compounds having groups represented by _{-NH 3} ^{+ and ionic groups other than groups represented by -COO-} can exclude halogenated hydrocarbon compounds and those having hydrogen sulfide groups Compounds, and organic compounds with amino groups, alkoxy groups, and silicon atoms.

(3) Solvent

The solvent system is not particularly limited as long as it is a medium that can disperse the semiconductor fine particles, but it is preferably one that is difficult to dissolve the semiconductor fine particles.

The term "solvent" in this specification refers to a substance that obtains a liquid state at 1 atmosphere and 25°C (except for polymerizable compounds and polymers).

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-戊酮、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 solvent systems include esters such as methyl formate, ethyl formate, propyl formate, pentyl formate, methyl acetate, ethyl acetate, and pentyl acetate; γ-butyrolactone, acetone, dimethyl ketone, diisopropyl formate, etc. Butyl ketone, cyclopentanone, cyclohexanone, methyl cyclohexanone and other ketones; diethyl ether, methyl-tertiary-butyl ether, diisopropyl ether, dimethoxymethane, dimethoxymethane Ethane, 1,4-bis

Alkane, 1,3-dioxolane, 4-methyldioxolane, tetrahydrofuran, methyltetrahydrofuran, anisole, phenylethyl ether and other ethers; methanol, ethanol, 1-propanol, 2- Propanol, 1-butanol, 2-butanol, tertiary-butanol, 1-pentanone, 2-methyl-2-butanol, methoxypropanol, diacetone alcohol, cyclohexanol, 2- Fluoroethanol, 2,2,2-trifluoroethanol, 2,2,3,3-tetrafluoro-1-propanol and other alcohols; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol Glycol ethers such as monobutyl ether, ethylene glycol monoethyl ether acetate, triethylene glycol dimethyl ether; N-methyl-2-pyrrolidone, N,N-dimethylformamide , Acetamide, N,N-dimethylacetamide and other organic solvents with amide groups; organic solvents with nitrile groups such as acetonitrile, isobutyronitrile, propionitrile, and methoxyacetonitrile; ethylene 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, xylene, etc. ; Dimethyl sulfite 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, pentyl formate, methyl acetate, ethyl acetate, pentyl acetate and other esters; γ-butyrolactone, acetone, dimethyl ketone, diisopropyl Butyl ketone, cyclopentanone, cyclohexanone, methyl cyclohexanone and other ketones; diethyl ether, methyl-tertiary-butyl ether, diisopropyl ether, dimethoxymethane, dimethoxymethane Ethane, 1,4-bis

Alkane, 1,3-dioxolane, 4-methyldioxolane, tetrahydrofuran, methyltetrahydrofuran, anisole, phenylethyl ether and other ethers, acetonitrile, isobutyronitrile, propionitrile, methoxy Organic solvents with nitrile groups such as acetonitrile; organic solvents with carbonate groups such as ethylene carbonate and propylene carbonate; organic solvents with halogenated hydrocarbon groups such as dichloromethane and chloroform; n-pentane, cyclohexane Organic solvents with hydrocarbon groups such as alkanes, n-hexane, benzene, toluene, xylene, etc. have low polarity and are considered to be difficult to dissolve semiconductor particles. Therefore, organic solvents with halogenated hydrocarbon groups such as methylene chloride and chloroform are preferred; Hydrocarbon organic solvents such as alkanes, cyclohexane, n-hexane, benzene, toluene, and xylene are more preferable.

(4) At least one selected from the group consisting of polymerizable compounds and polymers

The polymerizable compound contained in the composition related to the present invention is not particularly limited, but it is preferable that the semiconductor fine particles have a low solubility in the polymerizable compound at the temperature for producing the aforementioned composition.

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

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

The polymer contained in the composition related to the present invention is not particularly limited, but at the temperature for producing the composition, it is preferable that the semiconductor fine particles have a low solubility to the polymer.

For example, in the case of production at room temperature and normal pressure, the aforementioned polymer system is not particularly limited, but examples include known polymers such as polystyrene and methacrylic resin. Among them, the polymer is preferably an acrylic resin. The acrylic resin system contains structural units derived from either or both of acrylate and methacrylate.

(4) In the structural unit of the polymerizable compound and polymer, when the acrylate and/or methacrylate and the structural unit derived therefrom are expressed in mole%, the ratio is 10% or more with respect to the total structural unit. It may be 30% or more, it may be 50% or more, it may be 80% or more, or it may be 100%.

(5) At least 1 selected from the group consisting of ammonia, amines, carboxylic acids, and these salts or ions

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

That is, the composition system related 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 in the group.

Ammonia, amines and carboxylic acids, and their salts or ions usually function as capping ligands. The so-called capping ligand is a compound that is adsorbed on the surface of the semiconductor compound and has the effect of stabilizing and dispersing the semiconductor compound in the composition. Examples of ammonia or amine ions or salts (ammonium salts, etc.) include ammonium cations represented by the general formula (A1) described later, and ammonium salts containing them. Examples of carboxylic acid ions or salts (carboxylates, etc.) include carboxylate anions represented by the general formula (A2) described below, and carboxylates containing them. The composition system related to the present invention may contain any one of ammonium salt, etc., and carboxylate, etc., or both.

The ammonium salt may be, for example, an ammonium salt containing an ammonium cation represented by the general formula (A1).

In the general formula (A1), R ¹ to R ³ represent a hydrogen atom, and R ⁴ represent a hydrogen atom or an organic group. When it is an organic group, R ⁴ is preferably a hydrocarbon group such as an alkyl group, a cycloalkyl group, and an unsaturated hydrocarbon group.

The alkyl group represented by R ⁴ may be linear or branched.

The ^{number of carbon atoms of the alkyl group represented by R 4} is usually from 1 to 20, preferably from 5 to 20, and more preferably from 8 to 20.

The cycloalkyl system represented by 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, and more preferably 3 to 11. The number of carbon atoms is the number of carbon atoms containing substituents.

The ^{unsaturated hydrocarbon group of R 4} may be linear or branched.

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

R ⁴ is preferably a hydrogen atom, an alkyl group, or an unsaturated hydrocarbon group. The unsaturated hydrocarbon group is preferably an alkenyl group. R ⁴ is preferably an alkenyl group having 8 to 20 carbon atoms.

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

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

The alkenyl group of R ^{4 is the linear or branched alkyl group exemplified in R 6} to R ⁹ , in which the single bond (CC) between the carbon atoms of any one of them is substituted with a double 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 Carbon group, 9-octadecenyl group.

Anionic relatively not particularly limited, but for example, such as ^{Br -, Cl -, I -} , F - ions of the halogen compounds, carboxylate ions and the like as preferred embodiments.

Preferred examples of the ammonium salt system having the ammonium cation represented by the general formula (A1) and the relative anion include n-octyl ammonium salt and oleyl ammonium salt.

Examples of the carboxylate series include carboxylates containing a carboxylate anion represented by the following general formula (A2).

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 preferable.

The alkyl group represented by R ⁵ may be linear or branched. The ^{number of carbon atoms of the alkyl group represented by R 5} is usually from 1 to 20, preferably from 5 to 20, and more preferably from 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, and more preferably 3 to 11. The number of carbon atoms also includes the number of carbon atoms of the substituent.

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

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

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 of R ^{5 include the alkyl groups exemplified in R 6} to R ⁹ .

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

Specific examples of the alkenyl group of R ^{5 include the alkenyl groups exemplified in R 1} to R ⁴ .

The carboxylate anion represented by the general formula (A2) is preferably an oleic acid anion. The relative ionic cation system of the carboxylate anion represented by the general formula (A2) is not particularly limited, but preferred examples include protons, alkali metal cations, alkaline earth metal cations, and ammonium cations.

<About the blending ratio of each ingredient>

The composition of this embodiment contains (1) and (2), and further contains at least one of (3) and (4).

(1) Semiconductor particles

(2) having a group represented by the ₃ ⁺ and -COO -NH ^- an ionic group of an organic compound other than the group represented by

(3) Solvent

(4) At least one selected from the group consisting of polymerizable compounds and polymers

The composition of this embodiment includes (1), (2), and (4').

(1) Semiconductor particles

(2) having a group represented by the ₃ ⁺ and -COO -NH ^- an ionic group of an organic compound other than the group represented by

(4’) Polymer

In the composition of this embodiment, the blending ratio of (1) and (2) should be such that the organic compound of (2) can improve the quantum yield. It can be in accordance with (1) and (2). The type, etc. are appropriately determined.

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

In the composition of this embodiment, when (1) the semiconductor fine particles are fine particles of a perovskite compound, and the organic compound of (2) is a compound having an anionic group represented by the general formula (A5), the perovskite compound is The molar ratio [(A5)/B] of the metal ion of B and the organic compound of (A5) is 1 to 1000, 10 to 500, or 100 to 300.

In the composition of this embodiment, (1) the semiconductor fine particles are fine particles of a perovskite compound, and the organic compound of (2) is a cationic group represented by the general formula (A6-1) or (A6-2) In the case of compound, the molar ratio of the metal ion of B of the perovskite compound and the organic compound of (A6-1) [(A6-1)/B], and the metal ion of B of the perovskite compound and (A6-2) ) The molar ratio of the organic compound [(A6-2)/B] is from 0.001 to 500, from 0.01 to 100, from 0.1 to 50, from 1 to 30, from 2 to 20, or from 3 to 15.

In another aspect of this embodiment, the molar ratio [(A6-1)/B] and the molar ratio [(A6-2)/B] are preferably 2-15.

(1) The range related to the blending ratio of (2) is the composition within the above-mentioned range, and the organic compound of (2) has the effect of increasing the quantum yield, which is preferable in terms of particularly good performance.

In the composition of the present embodiment, (1), and (3) and (4), or the blending ratio of both, is such that the luminescence effect generated by the semiconductor fine particles of (1) can be exerted well. That is, it can be appropriately determined according to the types of (1) to (4), etc.

In the composition of the present embodiment containing any one or both of (1), (2), and (3) and (4), any one of (1), (3) and (4) Or the mass ratio of the two [either or both of (1)/(3) and (4)] is 0.00001 to 10, may be 0.0001 to 1, or may be 0.0005 to 0.1.

(1), and (3) and (4). The range related to the blending ratio of either or both is a composition within the above range. It is difficult to produce agglomeration of the semiconductor fine particles of (1), and the luminescence is also good. The point of play is better.

In the composition of the present embodiment containing (1), (2), and (4'), the blending ratio of (1) and (4') is only produced by the semiconductor particles of (1) The extent to which the luminescence effect is well exerted is sufficient, and it can be appropriately determined according to the types of (1) and (4').

In the composition of this embodiment, the mass ratio [(1)/(4')] of (1) and (4') is 0.00001 to 10, which may be 0.0001 to 1, or may be 0.0005 to 0.1.

(1) The range related to the blending ratio of (4') is a composition within the above-mentioned range, and it is preferable in terms of good performance of luminescence.

<Method of manufacturing composition>

Hereinafter, the manufacturing method of the composition in the present invention will be described by showing embodiments. According to the manufacturing method of the composition of this embodiment, the composition of the embodiment related to the present invention can be manufactured. In addition, the composition system of the present invention is not limited to those manufactured in accordance with the composition manufacturing method of the following embodiments.

<(1) Manufacturing method of semiconductor microparticles>

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

The method of manufacturing the semiconductor microparticles may include, for example, a method of heating a mixture of a monomer or a compound of the element constituting the semiconductor microparticles and a fat-soluble solvent.

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

Examples of the fat-soluble solvent include nitrogen-containing compounds having a hydrocarbon group with 4 to 20 carbon atoms, and oxygen-containing compounds having a hydrocarbon group with 4 to 20 carbon atoms. 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; oils Unsaturated aliphatic hydrocarbon groups such as cyclopentyl and cyclohexyl; aromatic hydrocarbon groups such as phenyl, benzyl, naphthyl, naphthyl methyl, etc., among which saturated aliphatic hydrocarbon groups or unsaturated aliphatic groups Group hydrocarbon groups are preferred. Examples of nitrogen-containing compounds include amines or amines, and examples of oxygen-containing compounds include fatty acids. Among such fat-soluble solvents, nitrogen-containing compounds having hydrocarbon groups with 4 to 20 carbon atoms are preferred, such as n-butylamine, isobutylamine, n-pentylamine, n-hexylamine, octylamine, and decylamine. Alkyl amines such as base amine, dodecyl amine, hexadecyl amine, and octadecyl amine, and alkenyl amines such as oleyl amine are preferred. Such a fat-soluble solvent can be bonded to the surface of the particle, and the bonding mode can include, for example, chemical bonding such as covalent bonding, ionic bonding, coordination bonding, hydrogen bonding, and Van der Waals bonding.

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

In the method for preparing semiconductor microparticles of the present invention, the heated mixed liquid is cooled and separated into supernatant and precipitation. The separated semiconductor microparticles (precipitates) can also be placed in an organic solvent (such as chloroform, toluene, Hexane, n-butanol, etc.) is a solution containing semiconductor microparticles. Or after cooling the heated mixed liquid, it is separated into supernatant and sediment. The insoluble or poorly soluble solvent of nanoparticles (such as methanol, ethanol, acetone, acetonitrile, etc.) can be added to the supernatant after separation. A precipitate is generated, and the precipitate is collected and placed in the organic solvent to form a solution containing semiconductor microparticles.

(Method for manufacturing crystalline particles of perovskite compound)

The semiconductor microparticles of the perovskite compound related to the present invention are based on known documents (Nano Lett. 2015, 15, 3692-3696, ACSNano, 2015, 9, 4533-4542) as a reference, and can be obtained by the following method manufacture.

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

For example, the manufacturing method of the semiconductor microparticles of the perovskite compound related to the present invention may include, for example, a step including dissolving the B component, the X component, and the A component in a solvent to obtain a solution, and combining the resulting solution with the solvent (semiconductor microparticles). The solubility to the solvent is lower than the solvent used in the step of obtaining the solution) The manufacturing method of the mixing step.

More specifically, for example, a manufacturing method including the following steps: a step of dissolving a compound containing component B and component X, and a compound containing component A or component A and component X in a solvent to obtain a solution; and A step of mixing a solution and a solvent (the solubility of the semiconductor particles in this solvent is lower than the solvent used in the step of obtaining the solution).

In addition, for example, a manufacturing method including the following steps: a step of 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 to dissolve it to obtain a solution; And the step of cooling the resulting solution.

The following describes the manufacturing method including the steps of: 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; combining the resulting solution and the solvent (semiconductor The solubility of the microparticles in the solvent is lower than the solvent used in the step of obtaining the solution) the step of mixing.

In addition, the solubility means the solubility at the temperature of the mixing step.

The aforementioned manufacturing method preferably includes a step of adding a capping ligand from the viewpoint of enabling the semiconductor fine particles to be stabilized and dispersed. The capping ligand is preferably added before the aforementioned mixing step. The capping ligand can also be added to the solution after the A component, the B component and the X component are dissolved, or it can be added to the solvent (for semiconductor particles) This solvent has a lower solubility than the solvent used in the step of obtaining the solution), and can also be added to the solution after dissolving the A component, the B component, and the X component, and the solvent (the solubility of the semiconductor particles in the solvent is higher than the solvent obtained in the step of obtaining the solution. The solvent is lower) of the two.

The aforementioned manufacturing method preferably includes: after the aforementioned mixing step; the step of removing coarse particles by centrifugal separation, filtration, and the like. The size of the coarse particles removed by the aforementioned removal step is preferably 10 μm or more, more preferably 1 μm or more, and most preferably 500 nm or more.

The aforementioned step of mixing the solution and the solvent (the solubility of the semiconductor microparticles in this solvent is lower than the solvent used in the step of obtaining the solution) may be to drop the (I) solution into the solvent (the semiconductor microparticles for this solvent The solubility is lower than the solvent used in the step of obtaining the solution), or the step of dropping into the solvent in the (II) solution (the solubility of the semiconductor particles in this solvent is lower than the solvent used in the step of obtaining the solution) Step, but from the viewpoint of improving dispersibility, (I) is preferred.

At the time of dropping, it is preferable to perform stirring from the viewpoint of improving the dispersibility.

In the step of mixing the solution and the solvent (the solubility of the semiconductor particles in this solvent is lower than the solvent used in the step of obtaining the solution), the temperature is not particularly limited, but it is ensured that the compound with the perovskite crystal structure is easy to precipitate From a viewpoint, the range of -20 to 40 degreeC is preferable, and the range of -5 to 30 degreeC 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。 There are no particular limitations on the two types of solvents that have different solubility in the solvent of the semiconductor microparticles used in the foregoing manufacturing method, but examples include those selected from methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, and 2-propanol. Butanol, tertiary-butanol, 1-pentanone, 2-methyl-2-butanol, methoxypropanol, diacetone alcohol, cyclohexanol, 2-fluoroethanol, 2,2,2-tri Fluoroethanol, 2,2,3,3-tetrafluoro-1-propanol and other alcohols; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol mono Glycol ethers such as ethyl ether acetate and triethylene glycol dimethyl ether; N,N-dimethylformamide, acetamide, N,N-dimethylacetamide, etc. have an amide group Organic solvents; dimethyl sulfide, methyl formate, ethyl formate, propyl formate, pentyl formate, methyl acetate, ethyl acetate, pentyl 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-di

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

The solvent used in the step of obtaining the solution contained in the aforementioned manufacturing method is preferably a solvent with high solubility for the solvent of the semiconductor particles. For example, when the aforementioned step is performed at room temperature (10°C to 30°C), for example, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, tertiary-butanol, 1-pentanone, 2-methyl-2-butanol, methoxypropanol, diacetone alcohol , Cyclohexanol, 2-fluoroethanol, 2,2,2-trifluoroethanol, 2,2,3,3-tetrafluoro-1-propanol and other alcohols; ethylene glycol monomethyl ether, ethylene glycol Glycol ethers such as monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, triethylene glycol dimethyl ether; N,N-dimethylformamide, acetamide Organic solvents with amide groups such as amines and N,N-dimethylacetamide; dimethyl sulfide.

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 contained 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), for example, methyl formate Ester, ethyl formate, propyl formate, pentyl formate, methyl acetate, ethyl acetate, pentyl acetate and other esters; γ-butyrolactone, N-methyl-2-pyrrolidone, acetone, dimethyl Ketones, diisobutyl ketone, cyclopentanone, cyclohexanone, methylcyclohexanone 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, phenylethyl ether and other ethers; acetonitrile, isobutyronitrile, propionitrile, methoxy Organic solvents with nitrile groups such as acetonitrile; organic solvents with carbonate groups such as ethylene carbonate and propylene carbonate; organic solvents with halogenated hydrocarbon groups such as dichloromethane and chloroform; n-pentane, cyclohexane Organic solvents with hydrocarbon groups such as alkanes, n-hexane, benzene, toluene, and xylene.

Among the two types of solvents with different solubility, the difference in solubility is preferably 100 μg/solvent 100 g to 90 g/solvent 100 g, and more preferably 1 mg/solvent 100 g to 90 g/solvent 100 g. From the viewpoint of making the solubility difference of 100μg/solvent 100g to 90g/solvent 100g, 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 the solution is N , N-Dimethylacetamide and other organic solvents with amide groups or dimethyl sulfide, preferably the solvent used in the mixing step is dichloromethane, chloroform and other organic solvents with halogenated hydrocarbon groups; Organic solvents with hydrocarbon groups such as n-pentane, cyclohexane, n-hexane, benzene, toluene, and xylene.

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

Examples of the aforementioned solid-liquid separation method include methods such as filtration and methods using evaporation of solvents.

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

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

More specifically, for example, a manufacturing method including 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 to dissolve it to obtain a solution Step; and the step of cooling the resulting solution.

In the foregoing manufacturing method, the semiconductor microparticles related to the present invention can be precipitated by the difference in solubility caused by the temperature difference, and the semiconductor microparticles related to the present invention can be manufactured.

From the viewpoint that the semiconductor fine particles can be stabilized and dispersed, the aforementioned manufacturing method preferably includes a step of adding a capping ligand.

The aforementioned manufacturing method preferably includes a step of removing coarse particles by centrifugal separation, filtration, etc., after the step of cooling. The size of the coarse particles removed by the above removal step is preferably 10 μm or more, more preferably 1 μm or more, and most preferably 500 nm or more.

Here, the so-called high-temperature solvent is only required to contain the compound of the B component and the X component, and the solvent containing the A component or the compound of the A component and the X component at a temperature that can dissolve. For example, a solvent at 60 to 600°C is preferred. , A solvent at 80 to 400°C 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/minute, and more preferably 10°C to 150°C/minute.

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-戊酮、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 aforementioned manufacturing 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, but it may be, for example, methyl formate Ester, ethyl formate, propyl formate, pentyl formate, methyl acetate, ethyl acetate, pentyl acetate and other esters; γ-butyrolactone, N-methyl-2-pyrrolidone, acetone, dimethyl Ketones, diisobutyl ketone, cyclopentanone, cyclohexanone, methylcyclohexanone 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, phenylethyl ether and other ethers; methanol, ethanol, 1-propanol, 2- Propanol, 1-butanol, 2-butanol, tertiary-butanol, 1-pentanone, 2-methyl-2-butanol, methoxypropanol, diacetone alcohol, cyclohexanol, 2- Fluoroethanol, 2,2,2-trifluoroethanol, 2,2,3,3-tetrafluoro-1-propanol and other alcohols; 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 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 ethylene carbonate and propylene carbonate Solvents; dichloromethane, chloroform and other organic solvents with halogenated hydrocarbon groups; n-pentane, cyclohexane, n-hexane, benzene, toluene, xylene and other organic solvents with hydrocarbon groups; dimethyl sulfide, 1- Octadecene.

As a method of taking out the semiconductor particles from the dispersion liquid containing the semiconductor particles, for example, a method of performing solid-liquid separation and recovering only the semiconductor particles can be mentioned.

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

<Method for manufacturing composition containing (1), (2) and (3)>

For example, the method for producing a composition containing (1) semiconductor fine particles, (2) an organic compound having a group represented by _{-NH 3} ^{+ and an ionic group other than the group represented by -COO -} , and (3) a solvent can be exemplified Such as: (a) containing: (1) semiconductor fine particles, (2) an organic compound having a group represented by _{-NH 3} ⁺ and an ionic group other than the group represented by ^{-COO -, and (3) a solvent mixture} Steps of manufacturing method.

The foregoing step (a) is for example:

(a1) may be mixed after (1) Semiconductor fine particles, and (3) a solvent mixture (2) having a group represented by the ₃ ⁺ and -COO -NH ^- a step of an organic compound other than an ionic group represented by the group , (A2) can be after mixing (1) semiconductor fine particles and (2) an organic compound having a group shown by _{-NH 3} ^{+ and an ionic group other than the group shown by -COO -} , and then mixing (3) a solvent step.

From the viewpoint of improving the dispersibility of semiconductor fine particles, step (a) is preferably step (a1).

From the viewpoint of improving the dispersibility, it is preferable to perform stirring during mixing.

In the step of mixing (1) semiconductor fine particles, (2) an organic compound having a group represented by _{-NH 3} ^{+ and an ionic group other than the group represented by -COO -} , and (3) a solvent, the temperature is not particularly limited However, from the viewpoint of uniform mixing, the range of 0 to 100°C is preferred, and the range of 10 to 80°C is more preferred.

<Method for manufacturing composition containing (1), (2), (3) and (5)>

For example, (1) semiconductor particles, (2) _{organic compounds having groups other than -NH 3} ⁺ and ^{ionic groups other than -COO -} , (3) solvents, and (5) selected from ammonia The manufacturing method of at least one of the group consisting of amines, carboxylic acids, and these salts or ions may include, for example: (a') a manufacturing method including the following steps: mixing (1) semiconductor particles, (2) Organic compounds having ionic groups other than the groups shown by _{-NH 3} ^{+ and -COO -} , (3) solvents, and (5) selected from ammonia, amines and carboxylic acids, and the like The step of at least one of the group of salts or ions.

The foregoing step (a') is for example:

(a'1) After mixing (1) semiconductor fine particles and (3) solvent, it can be combined with (2) an organic compound having a group represented by _{-NH 3} ⁺ and an ionic group other than the group represented by ^{-COO -,} And (5) a mixture of at least one selected from the group consisting of ammonia, amines and carboxylic acids, and these salts or ions; (a'2) may contain (5) selected from ammonia, amines and carboxylic acids acid, and salts or ions of these into groups of at least one kind of mixed solvent (1) and the semiconductor fine particles (3) of, and (2) having the group represented by -NH ₃ ⁺ and -COO ^- the Mixture of organic compounds with ionic groups other than those shown.

From the viewpoint of improving the dispersibility of semiconductor fine particles, step (a') is preferably (a'2).

In (a'2), (5) semiconductor particles containing at least one selected from the group consisting of ammonia, amines and carboxylic acids, and salts or ions of these (1) semiconductor particles can be obtained by adding (5) ) At least one selected from the group consisting of ammonia, amines, carboxylic acids, and salts or ions of these is added to any of the steps included in the above-mentioned method of manufacturing semiconductor microparticles to produce, or is obtained by mixing (1) Semiconductor fine particles, and (5) are manufactured by at least one selected from the group consisting of ammonia, amine, carboxylic acid, and these salts or ions. From the viewpoint of improving the dispersibility of semiconductor microparticles, it is preferable to add it in any of the steps included in the (1) semiconductor microparticle manufacturing method. Thereby, for example, (5) semiconductor particles containing at least one selected from the group consisting of ammonia, amines, carboxylic acids, and salts or ions of these (1) semiconductor particles are formed as dispersed in (3) solvent The dispersion and (2) a mixture of an organic compound having a group represented by _{-NH 3} ^{+ and an ionic group other than the group represented by -COO-} can obtain the composition related to the present invention.

From the viewpoint of improving the dispersibility, it is preferable to perform stirring during mixing.

Mixing (1) semiconductor microparticles, (2) organic compounds having ionic groups other than the groups shown by _{-NH 3} ^{+ and -COO -} , (3) solvents, and (5) selected from ammonia, In the step of at least one of the group of amine, carboxylic acid, and these salts or ions, the temperature is not particularly limited. From the viewpoint of uniform mixing, the range of 0 to 100°C is preferred, and the range of 10 to The range of 80°C is more preferable.

<Method for manufacturing composition containing (1), (2) and (4)>

Comprising (1), (2) a method for producing the composition, and (4) may be for example of the hybrid system composed of (1) Semiconductor fine particles, (2) having the group represented by -NH ₃ ⁺ and -COO ^- of the group represented by other than The ionic organic compound, and (4) at least one method selected from the group consisting of polymerizable compounds and polymers.

Mixing (1) semiconductor fine particles, (2) organic compounds having ionic groups other than the groups shown by _{-NH 3} ^{+ and -COO -} , and (4) selected from polymerizable compounds and polymers From the viewpoint of improving the dispersibility of (1) semiconductor fine particles, the grouping of at least one step is preferably performed while stirring.

Mixing (1) semiconductor fine particles, (2) organic compounds having groups represented by _{-NH 3} ^{+ and ionic groups other than groups represented by -COO -} , and (4) selected from polymerizable compounds and polymers In at least one step of the group, the temperature is not particularly limited, but from the viewpoint of uniform mixing, the range of 0 to 100°C is preferred, and the range of 10 to 80°C is more preferred.

(1) Semiconductor fine particles, (2) Organic compounds having ionic groups other than the group shown by _{-NH 3} ^{+ and -COO -} , and (4) selected from the group consisting of polymerizable compounds and polymers A method of manufacturing at least one composition of the group, for example: (b) may be a manufacturing method including the following steps: using (1) in (4) at least one selected from the group consisting of polymerizable compounds and polymers (1) The step of dispersing semiconductor particles to obtain a dispersion; and mixing the obtained dispersion and (2) the step of an organic compound having a group shown by _{-NH 3} ⁺ and an ionic group other than the group shown by ^{-COO -; (} c) It can be a manufacturing method including the following steps: (2) having a group represented by _{-NH 3} ^{+ and -COO-in (4) at least one selected from the group consisting of polymerizable compounds and polymers} Steps of dispersing organic compounds with ionic groups other than those shown to obtain a dispersion; mixing the resulting dispersion and (1) the step of semiconductor fine particles; (d) can be a manufacturing method including the following steps: in (4) selected from the group consisting of a polymerizable compound and a polymer formed by at least one group manipulation (1) semiconductor fine particles, and (2) having the group represented by -NH ₃ ⁺ and -COO ^- an ionic group other than the group represented by The step of dispersing a mixture of organic compounds.

Among the manufacturing methods (b) to (d), from the viewpoint of improving the dispersibility of semiconductor fine particles, the manufacturing method (b) is preferred. By the foregoing method, the present invention allows the associated compositions obtained as (1) Semiconductor fine particles are dispersed in (4) of the dispersion, and (2) having the group represented by -NH ₃ ⁺ and -COO ^- of the group represented by A mixture of organic compounds with other ionic groups.

In the step of obtaining each dispersion contained in the manufacturing method of (b) to (d), (4) may be dropped into (1) and/or (2), or (1) and/or (2) ) Drop into (4).

From the viewpoint of improving dispersibility, it is preferable to drop (1) and/or (2) into (4).

(1) or (2) may be dripped into the dispersion, or the dispersion may be dripped into (1) or (2) in the steps of performing each mixing included in the manufacturing methods of (b) to (c).

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

When a polymer is used as the organic compound in (4), the polymer may also be a polymer dissolved in a solvent.

The solvent for dissolving the aforementioned polymer is not particularly limited as long as it can dissolve the resin (polymer), but it is preferably one that is difficult to dissolve in the semiconductor fine particles related to 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-戊酮、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 above-mentioned resin dissolving solvent may include, for example, methyl formate, ethyl formate, propyl formate, pentyl formate, methyl acetate, ethyl acetate, pentyl 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-di

Alkane, 1,3-dioxolane, 4-methyldioxolane, tetrahydrofuran, methyltetrahydrofuran, anisole, phenylethyl ether and other ethers; methanol, ethanol, 1-propanol, 2- Propanol, 1-butanol, 2-butanol, tertiary-butanol, 1-pentanone, 2-methyl-2-butanol, methoxypropanol, diacetone alcohol, cyclohexanol, 2- Fluoroethanol, 2,2,2-trifluoroethanol, 2,2,3,3-tetrafluoro-1-propanol and other alcohols; 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 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 ethylene carbonate and propylene 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; 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，因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, pentyl formate, methyl acetate, ethyl acetate, pentyl acetate and other esters; γ-butyrolactone, acetone, dimethyl ketone, diisobutyl Ketones such as ketones, cyclopentanone, cyclohexanone, methyl cyclohexanone; diethyl ether, methyl-tertiary-butyl ether, diisopropyl ether, dimethoxymethane, dimethoxyethyl Alkane, 1,4-bis

Alkane, 1,3-dioxolane, 4-methyldioxolane, tetrahydrofuran, methyltetrahydrofuran, anisole, phenylethyl ether and other ethers; acetonitrile, isobutyronitrile, propionitrile, methoxy Organic solvents with nitrile groups such as acetonitrile; carbonate-based organic solvents such as ethylene carbonate and propylene 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 are 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. ; Organic solvents with hydrocarbon groups such as n-pentane, cyclohexane, n-hexane, benzene, toluene, and xylene are more preferred.

<Method for manufacturing composition containing (1), (2), (4) and (5)>

Containing (1) semiconductor microparticles, (2) organic compounds having groups represented by _{-NH 3} ^{+ and ionic groups other than groups represented by -COO -} , (4) selected from the group consisting of polymerizable compounds and polymers At least one of the group, and (5) the method for producing a composition of at least one selected from the group consisting of ammonia, amines, carboxylic acids, and these salts or ions, except for addition (5) In addition to at least one selected from the group consisting of ammonia, amines, carboxylic acids, and salts or ions of these, it can be the manufacture of the composition containing (1), (2) and (4) as described The method is the same.

(5) At least one selected from the group consisting of ammonia, amines, carboxylic acids, and these salts or ions can be added in any of the steps included in the above-mentioned (1) semiconductor microparticle manufacturing method, or It is added in any of the steps in the above-mentioned method for producing a composition containing (1), (2) and (4).

(5) At least one selected from the group consisting of ammonia, amines, carboxylic acids, and salts or ions of these, from the viewpoint of improving the dispersibility of semiconductor microparticles, in terms of (1) semiconductor microparticle manufacturing method It is better to add any of the steps included. Thereby, for example, (1) semiconductor fine particles containing (5) at least one selected from the group consisting of ammonia, amines, carboxylic acids, and salts or ions of these are dispersed in (4) selected from the mixture of organic compound other than an ionic group represented by the group ^- the group of at least one type of dispersion, and (2) having the group represented by -NH ₃ ⁺ and -COO polymerizable compound and a polymer formed by , The composition related to the present invention can be obtained.

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

The manufacturing method of the composition containing (1), (2) and (4') and the total of (1), (2) and (4') is 90% by mass or more includes, for example, the following manufacturing methods: including The step of mixing (1) semiconductor fine particles, (2) an organic compound having a group represented by _{-NH 3} ^{+ and an ionic group other than the group represented by -COO -} , and a polymerizable compound; and polymerizing the polymerizable compound Step; and mixing (1) semiconductor fine particles, (2) an organic compound having a group represented by _{-NH 3} ^{+ and an ionic group other than the group represented by -COO -} , and a step of dissolving a polymer in a solvent, and The step of removing the solvent.

The step of mixing included in the aforementioned manufacturing method can be the same as the method of manufacturing the composition containing (1), (2), and (4), which has already been explained.

The aforementioned manufacturing method is for example

(b1) A manufacturing method that may include the steps of: dispersing (1) semiconductor fine particles in a polymerizable compound to obtain a dispersion; mixing the resulting dispersion with (2) having a group represented by _{-NH 3} ^{+ and-} COO ^- the step of organic compounds with ionic groups other than the groups shown; and the step of polymerizing polymerizable compounds.

(b2) A manufacturing method that can include the steps of: dispersing (1) semiconductor microparticles in a polymer dissolved in a solvent to obtain a dispersion; mixing the resulting dispersion with (2) having a -NH ₃ ⁺ And the step of organic compounds with ionic groups other than the groups shown by ^{-COO -; and the step of removing the solvent.}

(c1) A manufacturing method that may include the following steps: (2) An organic compound having a group represented by _{-NH 3} ⁺ and an ionic group other than the group represented by ^{-COO-is dispersed in a polymerizable compound to obtain a dispersion} The step; the step of mixing the obtained dispersion and (1) the semiconductor fine particles; and the step of polymerizing the polymerizable compound.

(c2) A manufacturing method that may include the following steps: Disperse (2) an organic compound having a group represented by _{-NH 3} ⁺ and an ionic group other than the group represented by ^{-COO-in a polymer dissolved in a solvent,} The step of obtaining the dispersion; the step of mixing the obtained dispersion and (1) the semiconductor fine particles; and the step of removing the solvent.

(d1) may include the steps of a method for producing: the manipulation polymerizable compound (1) of the semiconductor fine particles, and (2) having the group represented by -NH ₃ ⁺ and -COO ^- an ionic group other than the organic group represented by The step of dispersing the mixture of compounds; and the step of polymerizing the polymerizable compound.

(d2) A manufacturing method that may include the following steps: (1) semiconductor microparticles and (2) have groups other than the groups shown by _{-NH 3} ^{+ and -COO-in a polymer dissolved in a solvent} The step of dispersing the mixture of base organic compounds; and the step of removing the solvent.

The step of removing the solvent included in the aforementioned manufacturing method may be a step of allowing it to stand at room temperature and allowing it to dry naturally, or it may also be a step of evaporating the solvent by drying under reduced pressure using a vacuum dryer or heating.

For example, it can 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 aforementioned production method can be carried out by appropriately using known polymerization reactions such as radical polymerization.

For example, during radical polymerization, it can be in (1) semiconductor fine particles, (2) organic compounds having ionic groups other than the groups shown by _{-NH 3} ^{+ and -COO -, and mixtures of polymerizable compounds} A radical polymerization initiator is added to generate free radicals to proceed the polymerization reaction.

The radical polymerization initiator system is not particularly limited, and, for example, a photoradical polymerization initiator can be mentioned.

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

<Method for manufacturing a composition containing (1), (2), (5) and (4') and the total of (1), (2), (4') and (5) is 90% by mass or more>

A method of manufacturing a composition that contains (1), (2), (5) and (4') and the total of (1), (2), (4') and (5) is 90% by mass or more, for example, in addition to Addition of (5) at least one selected from the group consisting of ammonia, amines, carboxylic acids, and these salts or ions, and may contain (1), (2), and (4') as described And the method of manufacturing a composition whose total of (1), (2) and (4') is 90% by mass or more is the same.

(5) At least one selected from the group consisting of ammonia, amines, carboxylic acids, and these salts or ions, which can be added in any of the steps in the above-mentioned (1) semiconductor microparticle manufacturing method, or It can be added in the step of mixing the above-mentioned (1) semiconductor fine particles, (2) an organic compound having a group represented by _{-NH 3} ⁺ and an ionic group other than the group represented by ^{-COO -, and a polymerizable compound,}

It can be added in the step of mixing the above-mentioned (1) semiconductor fine particles, (2) an organic compound having a group shown by _{-NH 3} ⁺ and an ionic group other than the group shown by ^{-COO -, and a polymer dissolved in a solvent} .

(5) At least one selected from the group consisting of ammonia, amines, carboxylic acids, and these salts or ions. From the viewpoint of improving the dispersibility of semiconductor particles, it is preferably used in (1) Manufacturing of semiconductor particles Add any step contained in the method.

≪Measurement of semiconductor particles≫

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

The semiconductor fine particles are dissolved in a good solvent such as N,N-dimethylformamide and then measured.

≪Measurement of quantum yield≫

The quantum yield of the composition containing the semiconductor microparticles related to the present invention is measured using an absolute PL quantum yield measuring device (for example, manufactured by Hamamatsu Photonics, trade name C9920-02) under excitation light 450 nm, room temperature, and atmosphere.

(1) Organic compounds containing semiconductor microparticles and (2) having groups represented by _{-NH 3} ^{+ and ionic groups other than groups represented by -COO -} , and further containing (3) a solvent-based composition so that The mixing ratio was adjusted so that the concentration of the semiconductor fine particles contained in the composition became 200 ppm (μg/g) and measured.

(1) Organic compounds containing semiconductor microparticles and (2) having groups represented by _{-NH 3} ^{+ and ionic groups other than groups represented by -COO -} , and further containing (4) selected from polymerizable compounds and polymers In the composition of at least one type in the group, the mixing ratio is adjusted so that the concentration of the semiconductor fine particles contained in the composition becomes 1000 μg/mL, and the measurement is performed. The same applies when substituting (4) with (4').

The composition of the present embodiment has a quantum yield of 32% or more as measured by the above-mentioned measuring method, and may be 40% or more, 50% or more, or 60% or more.

The composition of this embodiment has a quantum yield of 100% or less as measured by the above-mentioned measuring method, which can be 95% or less, 90% or less, 80% or less, or 70% or less , It can also be less than 65%.

The above upper limit and lower limit can be combined arbitrarily.

In one aspect of the present invention, the quantum yield of the composition of the present 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% The above 100% is even more preferable, and the above 60% and 100% are particularly preferable.

In another aspect of the present invention, the quantum yield of the composition of the present 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 40% or more. Above% and below 80% is even better. In addition, the aforementioned quantum yield may be 50% or more and 70% or less, or 60% or more and 65% or less.

<membrane>

The film system related to the present invention contains (1), (2), and (4'), and the total content of (1), (2) and (4') is 90% by mass or more relative to the total mass of the composition The film composed of things.

(1) Semiconductor particles

(2) having a group represented by the ₃ ⁺ and -COO -NH ^- an organic compound other than an ionic group represented by the group

(4’) Polymer

The shape of the film is not particularly limited, and may be a sheet shape, a rod shape, or the like. The "rod-shaped shape" in this specification means, for example, an anisotropic shape. The shape with anisotropy can exemplify the shape of a plate with different sides in length.

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

The thickness of the aforementioned film in this specification is obtained by measuring arbitrary 3 points with a micrometer and calculating the average value.

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

The film manufacturing method can obtain the film formed on the substrate by the manufacturing method (i) to (iV) of the manufacturing method of the laminated structure mentioned later, for example.

<Layered Structure>

The layered structure system related to the present invention has plural layers, and at least one layer is

A layered layer composed of a composition that contains (1), (2) and (4') and the total content of (1), (2) and (4') is 90% by mass or more relative to the total mass of the composition Construct.

(1) Semiconductor particles

(2) having a group represented by the ₃ ⁺ and -COO -NH ^- the organic compound having an ionic group other than the group represented by

(4’) Polymer

The composition system containing (1), (2) and (4') may further contain (5) at least one selected from the group consisting of ammonia, amine and carboxylic acid, and these salts or ions.

In the plural layers of the laminated structure, (1), (2) and (4') are contained, and the total content of (1), (2) and (4') is 90% by mass or more relative to the total mass of the composition Examples of layers other than the layer formed by the composition include any layers such as a substrate, a barrier layer, and a light scattering layer.

The shape of the laminated composition is not particularly limited, and may be any shape such as a sheet shape and 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 may have is not particularly limited, and for example, a substrate may be mentioned.

The substrate is not particularly limited, and it may also be a film. From the viewpoint of taking out light when emitting light, a transparent one is preferred. As the substrate, known materials such as plastics such as polyethylene terephthalate, and glass can be used.

For example, in a laminated structure, the total content of (1), (2) and (4') and the total content of (1), (2) and (4') is 90% by mass or more relative to the total mass of the composition. The layer 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. In the first build-up structure 1a, the film 10 of this embodiment is provided between the first substrate 20 and the second substrate 21. The film 10 is sealed by a 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, a film 10 related to this embodiment located between the first substrate 20 and the second substrate 21, and a sealing layer 22 of the laminated structure, and the sealing layer is disposed on the surface of the film 10 that is not in contact with the first substrate 20 and the second substrate 21.

(Barrier layer)

The layer system that the laminated structure according to the present invention may have is not particularly limited, and for example, a barrier layer may be mentioned. In order to protect the aforementioned composition from outside water vapor and atmospheric air, a barrier layer may also be included.

The barrier layer is not particularly limited. From the viewpoint of extracting light after luminescence, a transparent barrier layer is preferred. For example, a known barrier layer such as a polymer such as polyethylene terephthalate and a glass film 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 for example, a light scattering layer can be mentioned. From the viewpoint of efficiently absorbing incident light, a light scattering layer may be included.

The light-scattering layer is not particularly limited. From the viewpoint of extracting light after luminescence, a transparent light-scattering layer is preferred. For example, light-scattering particles such as silicon oxide particles, and a widening diffusion film can be applied to known light-scattering layers.

<Method of Manufacturing Laminated Structure>

The manufacturing method of the laminated structure can be, for example

(i) A manufacturing method of a laminated structure including the following steps: mixing (1) semiconductor microparticles, (2) organic compounds having groups represented by _{-NH 3} ⁺ and ionic groups other than groups represented by ^{-COO -,} And (3) the step of solvent and (4') polymer; the step of coating the obtained composition on the substrate; the step of removing the solvent.

(ii) A manufacturing method of a laminated structure including the following steps: mixing (1) semiconductor fine particles, (2) organic compounds having groups represented by _{-NH 3} ⁺ and ionic groups other than groups represented by ^{-COO -,} And the step of dissolving the polymer in the solvent; the step of coating the obtained composition on the substrate; the step of removing the solvent.

(iii) The manufacturing method of the laminated structure including the following steps: the composition of (1), (2) and (4') and (1), (2) and (4') in total is 90% by mass or more The step of attaching to the substrate; (1) semiconductor microparticles, (2) organic compounds with ionic groups other than the groups shown by _{-NH 3} ^{+ and -COO -, (4') polymers, (} iv) A manufacturing method of a laminated structure comprising the following steps: mixing (1) semiconductor fine particles, (2) an organic compound having a group represented by _{-NH 3} ⁺ and an ionic group other than the group represented by ^{-COO -, and} The step of polymerizing compound; the step of coating the obtained composition on the substrate; and the step of polymerizing the polymerizable compound.

The step of mixing and the step of removing the solvent included in the manufacturing method of (i), the step of mixing and the step of removing solvent included in the manufacturing method of (ii), and the manufacturing method of (iv) The step of mixing and the step of polymerizing the polymerizable compound can be the sum of (1), (2), and (4') and (1), (2), and (4'), respectively, as described. It is the same step as the steps included in the manufacturing method of the composition of 90% by mass or more.

The steps of coating on the substrate contained in the manufacturing methods of (i), (ii), and (iv) are particularly limited, but gravure coating, rod coating, printing, spraying, spin coating can be used Well-known coating methods such as method, dipping method, and die-slit coating method.

In the step of attaching to the substrate included in the manufacturing method of (iii), any adhesive can be used.

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

The manufacturing method of the laminated structure is a manufacturing method which may include the step of further attaching arbitrary films to the laminated structure obtained by (i) to (iv).

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

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

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

<Light-emitting device>

The light-emitting device according to the present invention can be obtained by combining the aforementioned composition, or the aforementioned multilayer structure, and a light source. The light-emitting device related to the present invention is a device that irradiates light from a light source to the aforementioned composition arranged in the rear stage, so that the aforementioned composition emits light, and extracts the light. The multilayer structure in the aforementioned light-emitting device may contain layers such as a reflective film, a diffusion film, a brightness enhancement portion, a sliver sheet, 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 thin film 50, a light guide plate 60, the aforementioned first laminated structure 1a, 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 making the aforementioned composition or the semiconductor fine particles in the multilayer structure emit light, a light source having an emission wavelength of 600 nm or less is preferred, for example, Known light sources such as light emitting diodes (LED) such as blue light emitting diodes, lasers, and EL can be used.

(Reflective film)

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

The reflective film is not particularly limited, but may include any suitable known materials such as a mirror, a film that reflects 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 the light from the light source or the light emitted from the aforementioned composition. The diffusion film system may include any diffusion film known in the aforementioned technical field, such as a widening diffusion film.

(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.

(稜鏡片)

The representative of the scallop sheet has a base material part and a scallop part. In addition, the base material part may be omitted according to adjacent members. The sheet can be attached to adjacent members via any appropriate adhesive layer (for example, adhesive layer, adhesive layer). The 稜鏡 piece is formed by juxtaposing a plurality of unit 稜鏡s which are convex on the side opposite to the identification side (the back side). By arranging the convex part of the scallop sheet toward the back side, the light passing through the scallop sheet can be easily condensed. In addition, if the convex portion of the ridge sheet is arranged toward the back side, compared with arranging the convex portion toward the recognition side, less light is not incident on the ridge sheet and reflected, and a high-brightness display can be obtained.

(Light guide plate)

Any appropriate light guide plate can be used for the light guide plate system. For example, it can be used for a light guide plate with a lens pattern formed on the back side, a light guide plate with a ridge shape on the back side and/or the recognition side, etc., in a way that the light from the lateral direction can be deflected to the thickness direction.

(Media material layer between components)

The light-emitting device related to the present invention is not particularly limited, and the optical path between adjacent members (layers) may include one or more layers composed of dielectric materials. More than one medium includes vacuum, air, gas, optical materials, adhesives, optical adhesives, glass, polymers, solids, liquids, gels, hardening materials, optical bonding materials, refractive index conformity or refractive index unconformity Materials, refractive index gradient materials, covering or anti-covering materials, spacers, silica gel, brightness enhancement materials, scattering or diffusion materials, reflective or anti-reflective materials, wavelength selective materials, wavelength selective anti-reflective materials, color filters The sheet, or other suitable medium known in the aforementioned technical field, but is not limited to these, and may include any suitable material.

Specific examples of the light-emitting device related to the present invention include, for example, those equipped with wavelength conversion materials for EL displays or liquid crystal displays.

Specifically, for example: (1) The composition of the present invention is placed in a glass tube, etc. and sealed, and this is arranged along the end surface (side) of the light guide plate on the blue light-emitting diode and the guide of the light source. Between the light plates, a backlight that converts blue light into green light or red light (side-lighting backlight), (2) the composition related to the present invention is thinned, and the two barrier films are sandwiched and sealed. The film is set on the light guide plate, from the blue light emitting diode placed on the end surface (side) of the light guide plate through the light guide plate to irradiate the blue light of the aforementioned sheet into the backlight of green light or red light (surface packaging method) Backlight), (3) Disperse semiconductor particles in resin, etc., and set them near the light-emitting part of the blue light-emitting diode, and convert the irradiated blue light into green light or red light (backlight of embedded method), and (4) Disperse the semiconductor particles in the resist and set it on the color filter to convert the blue light irradiated from the light source into green light or red light as a backlight.

In addition, specific examples of the light-emitting device related to the present invention may include, for example, forming the composition of the present invention and disposing it at the back of the blue light-emitting diode of the light source to convert blue light into green light or red light to emit white light. illumination.

<Manufacturing Method of Light-emitting Device>

For example, a manufacturing method including the step of placing the aforementioned light source and the optical path from the light source to the back stage of the aforementioned composition or laminated structure can be mentioned.

<Display>

As shown in FIG. 2, the display 3 of this embodiment includes a liquid crystal panel 40 and the aforementioned light-emitting device 2 in order from the recognition side. The light-emitting device 2 includes a second laminated structure 1 b and a light source 30. The second build-up structure 1b is the first build-up structure 1a that is further provided with a scallop 50 and a light guide plate 60. A liquid crystal panel typically includes a liquid crystal cell, a recognition side polarizing plate arranged on the recognition side of the liquid crystal cell, and a back side polarizing plate arranged on the back side of the liquid crystal cell. The display system may be further equipped with any appropriate other components.

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

<LCD panel>

The above-mentioned liquid crystal panel typically includes a liquid crystal cell, a recognition side polarizing plate disposed on the recognition side of the liquid crystal cell, and a back side polarizing plate disposed on the back side of the liquid crystal cell. The identification-side polarizing plate and the back-side polarizing plate can be arranged with respective absorption axes substantially orthogonal or parallel.

(Liquid crystal cell)

The liquid crystal cell has a pair of substrates and a liquid crystal layer as a display medium sandwiched between the substrates. In a general configuration, one substrate is provided with color filters and black matrix, and the other substrate is provided with a switching element that regulates the electrical and optical characteristics of the liquid crystal, a scanning line that imparts a gate signal to the switching element, and Source signal signal line, pixel electrode and counter electrode. The spacing (cell gap) between the above-mentioned substrates can be controlled by spacers and the like. The side system in contact with the liquid crystal layer of the above-mentioned substrate may be provided with, for example, an alignment film composed of polyimide or the like.

(Polarizer)

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

Any appropriate polarizer can be used for the above-mentioned polarizer system. Examples include polyvinyl alcohol-based films, partially formalized polyvinyl alcohol-based films, ethylene/vinyl acetate copolymer-based partially saponified films, and other hydrophilic polymer films that absorb dichroic substances such as iodine or dichroic dyes. And uniaxially stretched, polyolefin-based oriented films such as dehydrated polyvinyl alcohol or dehydrated polyvinyl chloride. Among these, a polarizer that is uniaxially stretched by adsorbing dichroic substances such as iodine on a polyvinyl alcohol-based film has a high polarized dichroic ratio, which is particularly preferred.

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

<LED>

The composition system 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 related to the present invention can be, for example, mixed with the composition related to the present invention and conductive particles such as ZnS to be laminated in a film form, an n-type transport layer is layered on a single area, and a p-type transport layer is layered on a single side. In the laminated structure, the holes of the p-type semiconductor and the electrons of the n-type semiconductor eliminate the charges in the semiconductor particles contained in the composition of the junction surface to emit light by passing current.

<Solar battery>

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

The structure of the aforementioned solar cell is not particularly limited, and examples include a fluorine-doped tin oxide (FTO) substrate, a dense layer of titanium oxide, a porous alumina layer, an active layer containing a composition related to the present invention, and 2 ,2',7,7'-four-(N,N'-bis-p-methoxyphenylamine)-9,9'-spirodiaphyllum (spiro-OMeTAD) and other hole transport layers, and silver (Ag) Electrode solar cell.

The dense layer of titanium oxide 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 light absorption efficiency.

The composition related 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-mentioned embodiment, and various changes can be added within a range that does not deviate from the spirit of the present invention.

[Example]

Hereinafter, the present invention will be explained more specifically based on examples and comparative examples, but the present invention is not limited to the following examples.

(Synthesis of composition)

[Example 1]

0.814 g of cesium carbonate, 40 mL of 1-octadecene solvent, and 2.5 mL of oleic acid were mixed. It stirred with a magnetic stirrer, and heated at 150 degreeC for 1 hour while flowing nitrogen gas, and prepared the cesium carbonate solution.

Mix 0.276 g of lead bromide ( _{PbBr 2} ) with 20 mL of 1-octadecene solvent. After stirring with a magnetic stir bar and heating at a temperature of 120°C for 1 hour while flowing nitrogen gas, 2 mL of oleic acid and 2 mL of oleylamine were added. After heating to a temperature of 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 the temperature was lowered to room temperature.

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

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

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

After dispersing semiconductor fine particles in 5 mL of toluene, aliquot 50 μL of the dispersion liquid and disperse in 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 200 ppm (μg/g).

Then, in the dispersion liquid after the above-mentioned semiconductor fine particles are dispersed, tributylhexadecylphosphonium bromide is mixed so that the molar ratio becomes tributylhexadecylphosphonium bromide/Pb=0.295 to obtain a composition .

[Example 2]

The composition was obtained in the same manner as in Example 1 above except that tributylhexadecylphosphonium bromide/Pb=0.884.

[Example 3]

The composition was obtained in the same manner as in Example 1 above except that tributylhexadecylphosphonium bromide/Pb=1.47.

[Example 4]

The composition was obtained in the same manner as in Example 1 above except that tributylhexadecylphosphonium bromide/Pb=2.95.

[Example 5]

The composition was obtained in the same manner as in Example 1 above except that tributylhexadecylphosphonium bromide/Pb=8.84.

[Example 6]

The composition was obtained in the same manner as in Example 1 above except that tributylhexadecylphosphonium bromide/Pb=14.7.

[Example 7]

0.814 g of cesium carbonate, 40 mL of 1-octadecene solvent, and 2.5 mL of oleic acid were mixed. It stirred with a magnetic stirrer, and heated at 150 degreeC for 1 hour while flowing nitrogen gas, and prepared the cesium carbonate solution.

Mix 0.276 g of lead bromide ( _{PbBr 2} ) with 20 mL of 1-octadecene solvent. After stirring with a magnetic stir bar and heating at a temperature of 120°C for 1 hour while flowing nitrogen gas, 2 mL of oleic acid and 2 mL of oleylamine were added. After heating to a temperature of 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 the temperature was lowered to room temperature.

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

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

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

After dispersing semiconductor fine particles in 5 mL of toluene, aliquot 50 μL of the dispersion liquid and disperse in 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 200 ppm (μg/g).

Then, in the dispersion liquid in which the semiconductor fine particles are dispersed, sodium dodecyl sulfate is mixed so that the molar ratio becomes sodium dodecyl sulfate/Pb=156 to obtain a composition.

[Example 8]

Except for sodium dodecyl sulfate/Pb=259, the composition was obtained in the same manner as in Example 7 above.

[Comparative Example 1]

0.814 g of cesium carbonate, 40 mL of 1-octadecene solvent, and 2.5 mL of oleic acid were mixed. It stirred with a magnetic stirrer, and heated at 150 degreeC for 1 hour while flowing nitrogen gas, and prepared the cesium carbonate solution.

Mix 0.276 g of lead bromide ( _{PbBr 2} ) with 20 mL of 1-octadecene solvent. After stirring with a magnetic stir bar and heating at a temperature of 120°C for 1 hour while flowing nitrogen gas, 2 mL of oleic acid and 2 mL of oleylamine were added. After heating to a temperature of 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 the temperature was lowered to room temperature.

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

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

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

After dispersing semiconductor fine particles in 5 mL of toluene, aliquot 50 µL of the dispersion liquid and disperse in 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 200 ppm (μg/g).

(Measurement of semiconductor particles)

The concentration of the semiconductor fine particles in the composition obtained in the Examples and Comparative Examples is the dispersion liquid containing the semiconductor fine particles and the solvent obtained by redispersing them, respectively, and N,N-dimethylformamide is added 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 8 and Comparative Example 1 were measured using an absolute PL quantum yield measuring device (manufactured by Hamamatsu Photonics, trade name C9920-02, excitation light 450 nm, room temperature, under the atmosphere).

As shown in Table 1 below, the composition and quantum yield (%) of the compositions of Examples 1 to 8 and Comparative Example 1 are described. In Table 1, "organic compound with ionic group/Pb" means the molar ratio of the amount of organic compound with ionic group divided by the amount of Pb.

Figure 3 shows the results of Examples 1 to 6. Figure 4 shows the results of Examples 7 to 8.

From the above results, it can be confirmed that the composition systems related to Examples 1 to 8 to which the present invention is applied and the composition of Comparative Example 1 to which the present invention is not applied have excellent quantum yields.

(Composition)

[Example 9]

0.814 g of cesium carbonate, 40 mL of 1-octadecene solvent, and 2.5 mL of oleic acid were mixed. It stirred with a magnetic stirrer, and heated at 150 degreeC for 1 hour while flowing nitrogen gas, and prepared the cesium carbonate solution.

Mix 0.276 g of lead bromide ( _{PbBr 2} ) with 20 mL of 1-octadecene solvent. After stirring with a magnetic stir bar and heating at a temperature of 120°C for 1 hour while flowing nitrogen gas, 2 mL of oleic acid and 2 mL of oleylamine were added. After heating to a temperature of 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 the temperature was lowered to room temperature.

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

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

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

After dispersing the semiconductor fine particles in 5 mL of toluene, aliquot 500 μL of the dispersion liquid and disperse it in 4.5 mL of toluene to obtain a dispersion liquid containing the semiconductor fine particles and the solvent. The concentration of the perovskite compound measured by ICP-MS and ion chromatography was 1500 ppm (μg/g).

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

cm)中，進一步混合溴化三丁基十六碳基鏻。 After mixing 0.15 g of the above dispersion liquid containing semiconductor microparticles and solvent, and 0.913 g of the polymer dissolved solution, the molar ratio becomes tributylhexadecylphosphonium bromide/Pb=1.47. Cup of Making (4.5

cm), further mixing tributylhexadecylphosphonium bromide.

The toluene was evaporated by natural drying to obtain a composition with a concentration of the perovskite compound of 1000 μg/mL. The composition is cut into a size of 1cm×1cm.

[Comparative Example 2]

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

Mix 0.276 g of lead bromide ( _{PbBr 2} ) with 20 mL of 1-octadecene solvent. After stirring with a magnetic stir bar and heating at a temperature of 120°C for 1 hour while flowing nitrogen gas, 2 mL of oleic acid and 2 mL of oleylamine were added. After heating to a temperature of 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 the temperature was lowered to room temperature.

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

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

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

After dispersing the semiconductor fine particles in 5 mL of toluene, aliquot 500 μL of the dispersion liquid and disperse it in 4.5 mL of toluene to obtain a dispersion liquid containing the semiconductor fine particles and the solvent. The concentration of the perovskite compound measured by ICP-MS and ion chromatography was 1000 ppm (μg/g).

Then, methacrylic resin (PMMA, manufactured by Sumitomo Chemical Co., Sumipex/methacrylic resin, MH, molecular weight about 120,000, specific gravity 1.2g/ml) is mixed with methacrylic resin and toluene so that it becomes 16.5% by mass , Heat at 60°C for 3 hours to obtain a solution in which the polymer is dissolved.

cm)中混 合。 Put 0.15g of the above dispersion liquid containing semiconductor particles and solvent, and 0.913g of the solution after dissolving the polymer in an aluminum cup (4.5

cm) in the mix.

The toluene was evaporated by natural drying to obtain a composition with a concentration of the perovskite compound of 1000 μg/mL. The composition is cut into a size of 1cm×1cm.

(Measurement of semiconductor particles)

The concentration of the semiconductor fine particles in the composition obtained in the Examples and Comparative Examples is the dispersion liquid containing the semiconductor fine particles and the solvent obtained by redispersing them, respectively, and N,N-dimethylformamide is added 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 yield of the composition obtained in Example 9 and Comparative Example 2 was measured using an absolute PL quantum yield measuring device (manufactured by Hamamatsu Photonics, trade name C9920-02, excitation light 450 nm, room temperature, under the atmosphere).

In Table 2 below, the composition and quantum yield (%) of the composition of Example 9 and Comparative Example 2 are described. In Table 2, organic compound with ionic group/Pb means the molar ratio of the amount of organic compound with ionic group divided by the amount of Pb.

From the above results, comparing the composition of Example 9 to which the present invention is applied and the composition of Comparative Example 2 to which the present invention is not applied, it can be confirmed that it has an excellent quantum yield.

[Reference example 1]

After putting the composition described in Examples 1 to 9 in a glass tube, etc. and sealing, arrange this between the blue light-emitting diode of the light source and the light guide plate to produce blue light conversion of the blue light-emitting diode It becomes a backlight of green light or red light.

[Reference example 2]

The composition described in Examples 1 to 9 can be thinned to obtain a resin composition. The film, which is sandwiched by two barrier films and sealed, is placed on a light guide plate to produce a backlight, which will be placed on The blue light emitting diode on the end surface (side surface) of the light guide plate converts the blue light irradiated on the aforementioned sheet into green light or red light through the light guide plate.

[Reference example 3]

The compositions described in Examples 1 to 9 were placed near the light-emitting portion of a blue light-emitting diode to produce a backlight that converts the irradiated blue light into green light or red light.

[Reference example 4]

After mixing the compositions described in Examples 1 to 9 and the resist, the solvent is removed to obtain a wavelength conversion material. Manufacture the obtained wavelength conversion material between the blue light-emitting diode of the light source and the light guide plate, or the back stage of the OLED of the light source, and convert the blue light of the light source into green light or red light.

[Reference example 5]

The composition described in Examples 1 to 9 is mixed with conductive particles such as ZnS to form a film, an n-type transport layer is layered on a single area, and a p-type transport layer is layered on the other side to obtain an LED. By passing the current, the holes of the p-type semiconductor and the electrons of the n-type semiconductor can eliminate the charges in the semiconductor particles on the junction surface to make them emit light.

[Reference example 6]

On the surface of a fluorine-doped tin oxide (FTO) substrate, a dense layer of titanium oxide is laminated, a porous alumina layer is laminated thereon, and the composition described in Examples 1 to 9 is laminated on it, and the solvent is removed , Layer 2,2',7,7'-four-(N,N'-bis-p-methoxyphenylamine)-9,9'-spiro-OMeTAD (spiro-OMeTAD), etc. The hole transport layer is laminated with a silver (Ag) layer on it to produce a solar cell.

[Reference example 7]

After mixing the composition described in Examples 1 to 9 with the resin, the solvent was removed to form a resin composition containing the composition related to the present invention, and this was placed in the back stage of the blue light-emitting diode to produce a blue The light-emitting diode irradiates the blue light of the aforementioned resin molded body and converts it into green light or red light to emit white light for laser diode illumination.

[Industrial Utilization Possibility]

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

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

1a‧‧‧The first multi-layer structure

10‧‧‧membrane

20‧‧‧The first substrate

21‧‧‧Second substrate

22‧‧‧Sealing layer

Claims (9)

A luminescent composition containing (1) and (2), and at least one of (3) and (4); (1) semiconductor particles, (2) the following general formula (A6-1) The organic compound with cationic group shown,

Z ⁺ series means P ⁺ , R ¹⁵ series means alkyl group or cycloalkyl group, R ¹⁶ to R ¹⁸ series each independently represent a hydrogen atom, alkyl group or cycloalkyl group, (3) solvent, (4) selected from polymerizable compounds And at least one of the group of polymers. The composition described in item 1 of the scope of the patent application, wherein the aforementioned (1) is a fine particle of a perovskite compound with A, B and X as constituents; A is in the perovskite crystal structure and is located in B is the component of each vertex of the hexahedron at the center, and is a monovalent cation; X is the component located at each vertex of the octahedron centered on B in the perovskite crystal structure, selected from halogens One or more anions in the group consisting of compound ions and thiocyanate ions; B is in the perovskite crystal structure, and is located at the top The point hexahedron and the component at the center of the octahedron where X is arranged at the vertex are metal ions. The composition described in item 1 or 2 of the scope of the patent application further contains (5) at least one selected from the group consisting of ammonia, amines, carboxylic acids, and these salts or ions. A luminous composition containing the composition of (1), (2) and (4'), and the total content of (1), (2) and (4') is relative to the total mass of the aforementioned composition 90% by mass or more; (1) semiconductor fine particles, (2) an organic compound having a cationic group represented by the following general formula (A6-1),

The Z ⁺ system represents P ⁺ , the R ¹⁵ system represents an alkyl group or a cycloalkyl group, and the R ¹⁶ to R ¹⁸ systems each independently represent a hydrogen atom, an alkyl group or a cycloalkyl group, and a (4') polymer. The composition described in item 4 of the scope of the patent application further contains (5) at least one selected from the group consisting of ammonia, amines, carboxylic acids, and these salts or ions. A luminescent film is a film composed of the composition described in item 4 or 5 of the scope of patent application. A layered structure with multiple layers and at least one layer is the reason The layer composed of the composition described in item 4 or 5 of the scope of patent application. A light-emitting device is provided with the laminated structure described in item 7 of the scope of patent application. A display device having the laminated structure described in item 7 of the scope of patent application.

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