JP2016037483A - Binuclear complex and light-emitting device using the same, color conversion substrate and medical apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a binuclear complex having broad excitation spectrum in a wavelength of 250 nm to 450 nm by selecting kind of rare earth ion and sharp emission spectrum near wavelength of 610 nm, near wavelength of 540 nm and near wavelength of 640 nm and used as a red phosphor or a green phosphor, light-emitting device, a color conversion substrate and medical apparatus.SOLUTION: There is provided a binuclear complex having a basic skeleton which a first complex structure and a second complex structure make a pair, where the first complex structure and the second complex structure is made by chemical binding of a rare earth element cation to a carboxylate anion, one oxygen of the first complex structure binds the rare earth element cation in the first complex structure and another oxygen of the first complex structure binds the rare earth element cation in the first complex structure and the rare earth element cation in the second complex structure.SELECTED DRAWING: None

Description

  The present invention relates to a binuclear complex and a light emitting element, a color conversion substrate, and an electronic device using the same.

White light emitting diodes (LEDs) are used for display, illumination, backlights of display devices, and the like.
As the white LED, generally, a LED including a blue LED element, a green phosphor, and a red phosphor is used. The reason why the white LED having such a configuration is widely used is that when used for a backlight of a display device, it has excellent consistency with color filters corresponding to the three primary colors of RGB, when used for illumination, This is because there are advantages such as excellent color rendering.

As the white LED, for example, a blue LED element in a blue region having an emission peak wavelength of 420 nm to 480 nm, a green phosphor (SiAlON: Eu ²⁺ ) in a green region having an emission peak wavelength of 500 nm to 550 nm, and an emission peak wavelength And a red phosphor (CaAlSiN ₃ : Eu ²⁺ ) in a red region of 600 nm to 780 nm (for example, see Patent Document 1).
Here, FIG. 17 is a graph showing an example of the emission spectrum of the white LED.
However, as shown in FIG. 18, the above-mentioned red phosphor has a wide full width at half maximum of the emission spectrum, and the luminescent component exists in a deep red region longer than the emission main wavelength (near 650 nm). Since light in the deep red region (region longer than 650 nm) has low visibility, the human eye cannot feel the brightness of the light in that region, so the light in that region is lost. That is, the light in the deep red region causes the light emission efficiency of the white LED to decrease.

Conventionally, as the red phosphor, an inorganic base crystal doped with rare earth ions as a luminescent center has been used. As the rare earth ions, Eu ²⁺ (emission peak wavelength is in the red to green region) and Ce ³⁺ (emission peak wavelength is in the green to yellow region) are mainly used. The red phosphor emits light due to the transition between the 4f orbit-5d orbit of these rare earth ions. The emission of the red phosphor due to the transition between the 4f orbit and the 5d orbit is characterized by a broad emission spectrum due to the influence of the host crystal.
Further, the light emission of the red phosphor due to the transition between the 4f orbit and 4f orbit of rare earth ions is hardly affected by the host crystal due to the shielding effect by the 5s orbital or the 5p orbit existing outside the 4f orbit of rare earth ions. It is known that the emission spectrum becomes sharp. In particular, in the rare earth complex, due to the influence of the ligand coordinated to the rare earth ion, the transition between 4f orbit-4f orbital, which is essentially a forbidden transition, becomes an allowable transition, and the transition probability increases (high absorption rate, luminous efficiency) Is high).
As a white light source, a light source including a blue light source and a rare earth complex is known (see, for example, Patent Document 2).

Japanese Patent No. 3837588 Japanese Patent No. 3897110

However, since the absorption band of the rare earth complex exists in the ultraviolet region, it absorbs light emitted from an excitation light source (blue LED element) that emits near ultraviolet light (excitation wavelength: 405 nm) or blue light emission (excitation wavelength: 450 nm). It is impossible to excite and emit light.
Further, in the white LED of Patent Document 1, the excitation (absorption) spectrum of the red phosphor is broad, but the emission spectrum is also broad.
Furthermore, in the white light source of Patent Document 2, the emission spectrum of the rare earth complex is sharp due to the transition between the 4f orbital and 4f orbitals of the rare earth complex, but the excitation spectrum of the rare earth complex is also sharp. It is difficult to excite the rare earth complex due to the light emission. Therefore, it is necessary to match the emission peak wavelength of the blue light source according to the sharp excitation spectrum of the rare earth complex.

The present invention has been made in view of the above circumstances, and by selecting the type of rare earth ions, the excitation spectrum is broad at a wavelength of 250 nm to 450 nm, and the emission spectrum is sharp near a wavelength of 610 nm. An object of the present invention is to provide a binuclear complex used as a red phosphor, a light emitting element using the same, a color conversion substrate, and an electronic device.
In addition, the present invention provides a binuclear complex that is used as a green phosphor by selecting the type of rare earth ions, the excitation spectrum is broad at a wavelength of 250 nm to 450 nm, and the emission spectrum is sharp near a wavelength of 540 nm. Another object is to provide a light emitting element, a color conversion substrate, and an electronic device using the same.
In addition, the present invention provides a binuclear complex that is used as a red phosphor by selecting the type of rare earth ions, the excitation spectrum is broad in the wavelength range of 250 nm to 450 nm, and the emission spectrum is sharp in the vicinity of the wavelength of 640 nm. Another object is to provide a light emitting element, a color conversion substrate, and an electronic device using the same.

  The binuclear complex of one aspect of the present invention is a binuclear complex having a basic skeleton in which a first complex structure and a second complex structure are paired, and the first complex structure and the second complex structure. Is formed by chemically bonding a rare earth element cation to a carboxylate anion, and one oxygen of the first complex structure is bonded to the rare earth element cation in the first complex structure, and the other of the first complex structure is Oxygen is combined with the rare earth element cation in the first complex structure and the rare earth element cation in the second complex structure.

  In the binuclear complex of one embodiment of the present invention, the basic skeleton may be represented by the following general formula (1).

(In the formula, R represents a hydrogen atom, a deuterium atom, a hydrocarbon group represented by C _n H _m , or a group obtained by substituting H with another element from a hydrocarbon represented by C _n H _m X. A represents at least one cation selected from the group consisting of Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu, and X represents a halogen atom. Represents an oxygen atom, a nitrogen atom, a sulfur atom, or a phosphorus atom.)

  In the binuclear complex of one aspect of the present invention, each of the rare earth element cation of the first complex structure and the rare earth element cation of the second complex structure absorbs light, and the light energy is absorbed into the rare earth element cation. At least one photosensitizing ligand to be supplied to may be coordinate-bonded.

  In the binuclear complex of one aspect of the present invention, each of the rare earth element cation of the first complex structure and the rare earth element cation of the second complex structure absorbs light, and the light energy is absorbed into the rare earth element cation. Two or three photosensitizing ligands to be supplied to may be coordinate-bonded.

  In the binuclear complex of one embodiment of the present invention, the ligand may have at least π conjugation.

  In the binuclear complex of one aspect of the present invention, the ligand may be a bidentate ligand.

  In the binuclear complex of one embodiment of the present invention, the ligand may be represented by the following general formulas (2) to (4).

(In the formula, ^{R 1} and ^{R 2} are each _{independently} a C n _H hydrocarbon group represented by _m, C n _{H m} have been substituted by hydrocarbon H to another element represented by X D represents a hydrogen atom, a deuterium atom, a halogen atom, a hydrocarbon group represented by C _n H _m , or a group in which H is substituted with another element from a hydrocarbon represented by C _n H _m X X represents a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a selenium atom, or a phosphorus atom.)

(Wherein, ^{R 3} and ^{R 4} are each _{independently} a C n _H hydrocarbon group represented by _m, C n _{H m} have been substituted by hydrocarbon H to another element represented by X X represents a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a selenium atom, or a phosphorus atom.)

(Wherein, ^{R 5} and ^{R 6} are each _{independently} a C n _H hydrocarbon group represented by _m, C n _{H m} have been substituted by hydrocarbon H to another element represented by X X ¹ and X ² each independently represent a group IVb atom excluding carbon, a group Vb atom excluding nitrogen, and a group VIb atom excluding oxygen, and Y represents a halogen atom, oxygen atom, nitrogen atom, sulfur An atom, a selenium atom, or a phosphorus atom, and a and b each independently represent 0 or 1.)

  In the binuclear complex of one embodiment of the present invention, the ligand may be represented by the following general formula (5).

(In the formula, R ⁷ represents a hydrocarbon represented by C _n H _m , or a group obtained by substituting H with another element from a hydrocarbon represented by C _n H _m X. X ³ represents carbon. And represents a group IVb atom excluding nitrogen, a group Vb atom excluding nitrogen, and a group VIb atom excluding oxygen, and c represents 0 or 1.)

  A light-emitting element according to one aspect of the present invention includes a semiconductor light-emitting element, a resin surrounding the semiconductor light-emitting element, a dispersion dispersed in the resin, and excited by light emitted from the semiconductor light-emitting element. And at least two phosphors that emit fluorescence of different wavelengths, wherein one of the two phosphors is composed of the binuclear complex of one aspect of the present invention.

  In the light-emitting element of one embodiment of the present invention, an emission peak wavelength of light emitted from the semiconductor light-emitting element may be 380 nm or more and 470 nm or less.

  In the light-emitting element of one embodiment of the present invention, the binuclear complex includes at least Eu, the emission peak wavelength of the binuclear complex is 605 nm to 620 nm, and the full width at half maximum of the emission peak of the binuclear complex is 15 nm. It may be the following.

  In the light-emitting element of one embodiment of the present invention, the binuclear complex includes at least Tb, the emission peak wavelength of the binuclear complex is 535 nm or more and 550 nm or less, and the full width at half maximum of the emission peak of the binuclear complex is 15 nm. It may be the following.

  In the light-emitting element of one embodiment of the present invention, the binuclear complex contains at least Sm, the emission peak wavelength of the binuclear complex is 635 nm or more and 650 nm or less, and the full width at half maximum of the emission peak of the binuclear complex is 15 nm. It may be the following.

  A color conversion substrate according to an aspect of the present invention includes a transparent substrate having optical transparency, and a color conversion layer that is provided on one surface of the transparent substrate and is excited by external light to emit light having a wavelength different from the excitation wavelength. And the color conversion layer includes the binuclear complex according to any one of claims 1 to 8.

  In the color conversion substrate of one embodiment of the present invention, the emission peak wavelength of the external light may be 380 nm or more and 470 nm or less.

  In the color conversion substrate of one embodiment of the present invention, the binuclear complex contains at least Eu, the emission peak wavelength of the binuclear complex is 605 nm or more and 620 nm or less, and the full width at half maximum of the emission peak of the binuclear complex is It may be 15 nm or less.

  In the color conversion substrate of one aspect of the present invention, the binuclear complex contains at least Tb, the emission peak wavelength of the binuclear complex is 535 nm or more and 550 nm or less, and the full width at half maximum of the emission peak of the binuclear complex is It may be 15 nm or less.

  In the color conversion substrate of one embodiment of the present invention, the binuclear complex contains at least Sm, the emission peak wavelength of the binuclear complex is 635 nm or more and 650 nm or less, and the full width at half maximum of the emission peak of the binuclear complex is It may be 15 nm or less.

  An electronic apparatus according to one aspect of the present invention includes at least one of the light-emitting element according to one aspect of the present invention and the color conversion substrate according to one aspect of the present invention.

  According to the aspect of the present invention, by selecting the kind of rare earth ions, the excitation spectrum is broad at a wavelength of 250 nm to 450 nm, and the emission spectrum is sharp near a wavelength of 610 nm, near a wavelength of 540 nm, or near a wavelength of 640 nm. A binuclear complex used as a red phosphor or a green phosphor, and a light-emitting element, a color conversion substrate, and an electronic device using the same can be provided.

It is a molecular model which shows the basic skeleton of the binuclear complex which is 1st Embodiment of this invention. It is a molecular model which shows the binuclear complex which is 1st Embodiment of this invention. It is sectional drawing which shows schematic structure of a white light emitting diode as an example of the light emitting element which is 2nd Embodiment of this invention. It is sectional drawing which shows schematic structure of the color conversion board | substrate which is 3rd Embodiment of this invention. It is a schematic perspective view which shows a ceiling light as a 1st example of the illuminating device which is 4th Embodiment of this invention. It is a schematic perspective view which shows an illumination stand as a 2nd example of the illuminating device which is 4th Embodiment of this invention. It is a schematic front view which shows a mobile telephone as a 1st example of the electronic device which is 5th Embodiment of this invention. It is a schematic front view which shows a thin television as a 2nd example of the electronic device which is 5th Embodiment of this invention. It is a schematic front view which shows a portable game machine as the 3rd example of the electronic device which is 5th Embodiment of this invention. It is a schematic perspective view which shows a notebook computer as a 4th example of the electronic device which is 5th Embodiment of this invention. ₂ is a graph showing measurement results of excitation spectra of Eu ³⁺ rare earth complex [Eu (C ₅ O ₂ H ₂ F ₆ ) ₃ .nH ₂ O] obtained in Example 1. FIG. 4 is a graph showing a measurement result of an emission spectrum of Eu ³⁺ rare earth complex [Eu (C ₅ O ₂ H ₂ F ₆ ) ₃ .nH ₂ O] obtained in Example 1. 4 is a graph showing the measurement results of the excitation spectrum of Tb ³⁺ rare earth complex [Eu (C ₅ O ₂ H ₂ F ₆ ) ₃ .nH ₂ O] obtained in Example 2. 4 is a graph showing a measurement result of an emission spectrum of Tb ³⁺ rare earth complex [Eu (C ₅ O ₂ H ₂ F ₆ ) ₃ · nH ₂ O] obtained in Example 2. ₆ is a graph showing the measurement results of the excitation spectrum of Sm ³⁺ rare earth complex [Eu (C ₅ O ₂ H ₂ F ₆ ) ₃ .nH ₂ O] obtained in Example 3. 4 is a graph showing a measurement result of an emission spectrum of Sm ³⁺ rare earth complex [Eu (C ₅ O ₂ H ₂ F ₆ ) ₃ .nH ₂ O] obtained in Example 3. It is a graph which shows an example of the emission spectrum of white LED using the conventional red fluorescent substance. It is a graph which shows an example of the emission spectrum of the conventional red fluorescent substance.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
In all of the following drawings, in order to make each component easy to see, the scale of the size may be changed depending on the component.
Further, the present embodiment is specifically described in order to make the gist of the invention better understood, and does not limit the present invention unless otherwise specified.

[First Embodiment] (Binuclear Complex)
The binuclear complex of the present embodiment is a binuclear complex having a basic skeleton in which a first complex structure and a second complex structure are paired, and the first complex structure and the second complex structure are carboxylate anions. The rare earth element cations are chemically bonded to each other, one oxygen of the first complex structure is bonded to the rare earth element cations in the first complex structure, and the other oxygen of the first complex structure is bonded to the first complex structure. The rare earth element cation is bonded to the rare earth element cation in the second complex structure.

In the binuclear complex of the present embodiment, the basic skeleton is composed of, for example, a compound represented by the following general formula (1) and FIG. In FIG. 1, R is a methyl group (—CH ₃ ).

(In the formula, R represents a hydrogen atom, a deuterium atom, a hydrocarbon group represented by C _n H _m , or a group obtained by substituting H with another element from a hydrocarbon represented by C _n H _m X. A represents at least one cation selected from the group consisting of Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu, and X represents a halogen atom. Represents an oxygen atom, a nitrogen atom, a sulfur atom, or a phosphorus atom.)

That is, the binuclear complex of the present embodiment has a structure in which two rare earth element cations A are connected by two carboxylate anions RCOO ⁻ .

  In the general formula (1), examples of the halogen atom represented by X include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

In the general formula (1), when R is a group obtained by substituting the hydrocarbon represented by _C n hydrocarbon radical or a _C represented by _{H m} n _{H m} X H to other _{elements, C} n H _The hydrocarbon group represented by _m or the group represented by C _n H _m X substituted with H by another element is, for example, an alkyl group, an alkylene group, an alkynyl group, an aryl group, a heteroaryl group, etc. Is mentioned.
The alkyl group may be linear, branched or cyclic. When the alkyl group is cyclic, it may be monocyclic or polycyclic.

  Examples of linear or branched alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, and n-pentyl. Group, isopentyl group, neopentyl group, tert-pentyl group, 1-methylbutyl group, n-hexyl group, 2-methylpentyl group, 3-methylpentyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group N-heptyl group, 2-methylhexyl group, 3-methylhexyl group, 2,2-dimethylpentyl group, 2,3-dimethylpentyl group, 2,4-dimethylpentyl group, 3,3-dimethylpentyl group, 3-ethylpentyl group, 2,2,3-trimethylbutyl group, n-octyl group, isooctyl group, nonyl group, decyl group, undecyl group, dodecyl group Group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, heneicosyl group, docosyl group.

  Examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, a norbornyl group, an isobornyl group, a 1-adamantyl group, and a 2-adamantyl group. Group, tricyclodecyl group and the like. Furthermore, examples of the alkyl group include those in which one or more hydrogen atoms of these cyclic alkyl groups are substituted with a linear, branched or cyclic alkyl group.

  Further, one or more hydrogen atoms in the alkyl group may be optionally substituted with a halogen atom. Examples of the halogen atom substituted for the hydrogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

  In the general formula (1), the alkylene group represented by R may be linear, branched or cyclic. When the alkylene group is cyclic, it may be monocyclic or polycyclic.

  Examples of the linear or branched alkylene group include methylene group, ethylene group, n-propylene group, n-butylene group, n-hexylene group, n-heptylene group, n-octylene group and n-dodecylene. Groups and the like.

  One or more hydrogen atoms in the alkylene group may be optionally substituted with a halogen atom. Examples of the halogen atom substituted for the hydrogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

  In the general formula (1), the alkynyl group represented by R may be linear, branched or cyclic. When the alkynyl group is cyclic, it may be monocyclic or polycyclic.

  Examples of the linear or branched alkynyl group include ethynyl group, 2-propynyl group (propargyl group) and the like.

  One or more hydrogen atoms in the alkynyl group may be optionally substituted with a halogen atom. Examples of the halogen atom substituted for the hydrogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

  In the general formula (1), the aryl group represented by R may be monocyclic or polycyclic.

  Examples of the aryl group include a phenyl group, 1-naphthyl group, 2-naphthyl group, o-tolyl group, m-tolyl group, p-tolyl group, xylyl group (dimethylphenyl group) and the like. One or more hydrogen atoms of these aryl groups may be further substituted with these aryl groups or the above alkyl group represented by R.

In the general formula (1), as the heteroaryl group represented by R, among the aryl groups represented by R, one or more carbon atoms constituting the aromatic ring skeleton or the carbon atom is bonded to this. In the group substituted with a heteroatom together with a hydrogen atom and an aromatic group and a cyclic alkyl group in R, one or more single bonds (C—C) between carbon atoms are double bonds ( C = C) and further substituted with one or more carbon atoms constituting the ring skeleton, or a hydrogen atom bonded to the carbon atom, and a heteroatom, and has aromaticity Groups.
Preferred examples of the hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom, a selenium atom, and a phosphorus atom. The number of heteroatoms constituting the aromatic ring skeleton is not particularly limited, but is preferably 1 to 2. When the number of heteroatoms constituting the aromatic ring skeleton is 2 or more, the plurality of heteroatoms may be all the same, all different, or only partly the same. May be.

  When the binuclear complex having the compound represented by the general formula (1) as a basic skeleton has an alkyl group as R, the solubility in a solvent is improved by selecting an appropriate solvent. By using a binuclear complex having high solubility in a solvent, the handleability of the binuclear complex is further improved. For example, a light emitting element described later can easily obtain a light emitting efficiency.

A represents a cation of a rare earth element, specifically, cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), Cation of at least one rare earth element selected from the group consisting of terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), yttrium (Yb) and lutesium (Lu) ( Rare earth element cations).
The rare earth element cation is usually a trivalent cation, but may be a divalent or tetravalent cation.

These rare earth element cations may be used alone or in combination of two or more.
Two or more rare earth element cations may be used in combination, but at least one rare earth element cation preferably has red emission (emission peak wavelength: 600 nm to 780 nm). The at least one rare earth element cation preferably has an emission peak wavelength of 600 nm to 650 nm. In view of this point (emission peak wavelength), samarium ions (Sm ³⁺ ) and erbium ions (Eu ³⁺ ) are preferred as the rare earth element cations.

  In the binuclear complex of the present embodiment, each of the rare earth element cation having the first complex structure and the rare earth element cation having the second complex structure absorbs light and supplies the light energy to the rare earth element cation. It is preferable that at least one ligand is coordinated.

  In the binuclear complex of the present embodiment, the photosensitizing ligand may be represented by the following general formulas (2) to (5).

(In the formula, ^{R 1} and ^{R 2} are each _{independently} a C n _H hydrocarbon group represented by _m, C n _{H m} have been substituted by hydrocarbon H to another element represented by X D represents a hydrogen atom, a deuterium atom, a halogen atom, a hydrocarbon group represented by C _n H _m , or a group in which H is substituted with another element from a hydrocarbon represented by C _n H _m X X represents a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a selenium atom, or a phosphorus atom.)

In the general formula (2), is a ^{group R 1} and ^{R 2} is substituted with _C n _{H m} hydrocarbon group or represented by _C n _{H m} X _H from hydrocarbon represented by the other elements , group substituted by a hydrocarbon H to another element represented by C _n H hydrocarbon group or a C _n represented by _{m H} m _X, for example, an alkyl group, an alkylene group, an alkynyl group, an aryl group, Heteroaryl group etc. are mentioned.
The alkyl group may be linear, branched or cyclic. When the alkyl group is cyclic, it may be monocyclic or polycyclic.

  Examples of linear or branched alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, and n-pentyl. Group, isopentyl group, neopentyl group, tert-pentyl group, 1-methylbutyl group, n-hexyl group, 2-methylpentyl group, 3-methylpentyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group N-heptyl group, 2-methylhexyl group, 3-methylhexyl group, 2,2-dimethylpentyl group, 2,3-dimethylpentyl group, 2,4-dimethylpentyl group, 3,3-dimethylpentyl group, 3-ethylpentyl group, 2,2,3-trimethylbutyl group, n-octyl group, isooctyl group, nonyl group, decyl group, undecyl group, dodecyl group Group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, heneicosyl group, docosyl group.

  Examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, a norbornyl group, an isobornyl group, a 1-adamantyl group, and a 2-adamantyl group. Group, tricyclodecyl group and the like. Furthermore, examples of the alkyl group include those in which one or more hydrogen atoms of these cyclic alkyl groups are substituted with a linear, branched or cyclic alkyl group.

  Further, one or more hydrogen atoms in the alkyl group may be optionally substituted with a halogen atom. Examples of the halogen atom substituted for the hydrogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

In the general formula (2), the alkylene group represented by R ¹ and R ² may be linear, branched or cyclic. When the alkylene group is cyclic, it may be monocyclic or polycyclic.

  Examples of the linear or branched alkylene group include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-hexylene group, an n-heptylene group, an n-octylene group, and an n-dodecylene group. Etc.

  One or more hydrogen atoms in the alkylene group may be optionally substituted with a halogen atom. Examples of the halogen atom substituted for the hydrogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

In the above general formula (2), the alkynyl group represented by R ¹ and R ² may be linear, branched or cyclic. When the alkynyl group is cyclic, it may be monocyclic or polycyclic.

  Examples of the linear or branched alkynyl group include ethynyl group, 2-propynyl group (propargyl group) and the like.

  One or more hydrogen atoms in the alkynyl group may be optionally substituted with a halogen atom. Examples of the halogen atom substituted for the hydrogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

In the general formula (2), the aryl group represented by R ¹ and R ² may be monocyclic or polycyclic.

Examples of the aryl group include a phenyl group, 1-naphthyl group, 2-naphthyl group, o-tolyl group, m-tolyl group, p-tolyl group, xylyl group (dimethylphenyl group) and the like. One or more hydrogen atoms of these aryl groups may be further substituted with these aryl groups or the above alkyl groups represented by R ¹ and R ² .

In the general formula (2), as the heteroaryl group represented by R ¹ and R ^2, of the aryl group represented by R ¹ and R ^2, 1 or more carbon atoms constituting the aromatic ring skeleton, or In the group in which the carbon atom is substituted with a heteroatom together with a hydrogen atom bonded thereto and has aromaticity, and in the cyclic alkyl group in R ¹ and R ² , one or more carbon atoms Together with one or more carbon atoms constituting a ring skeleton, or a hydrogen atom with which the carbon atom is bonded to the single bond (C—C) of And a group substituted with a heteroatom and having aromaticity.
Preferred examples of the hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom, a selenium atom, and a phosphorus atom. The number of heteroatoms constituting the aromatic ring skeleton is not particularly limited, but is preferably 1 to 2. When the number of heteroatoms constituting the aromatic ring skeleton is 2 or more, the plurality of heteroatoms may be all the same, all different, or only partly the same. May be.

  In the general formula (2), examples of the halogen atom represented by D include fluorine (F), chlorine (Cl), bromine (Br), and iodine (I).

  In the general formula (2), the alkyl group represented by D may be linear, branched or cyclic. When the alkyl group is cyclic, it may be monocyclic or polycyclic.

  Examples of linear or branched alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, and n-pentyl. Group, isopentyl group, neopentyl group, tert-pentyl group, 1-methylbutyl group, n-hexyl group, 2-methylpentyl group, 3-methylpentyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group N-heptyl group, 2-methylhexyl group, 3-methylhexyl group, 2,2-dimethylpentyl group, 2,3-dimethylpentyl group, 2,4-dimethylpentyl group, 3,3-dimethylpentyl group, 3-ethylpentyl group, 2,2,3-trimethylbutyl group, n-octyl group, isooctyl group, nonyl group, decyl group, undecyl group, dodecyl group Group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, heneicosyl group, docosyl group.

  Examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, a norbornyl group, an isobornyl group, a 1-adamantyl group, and a 2-adamantyl group. Group, tricyclodecyl group and the like. Furthermore, examples of the alkyl group include those in which one or more hydrogen atoms of these cyclic alkyl groups are substituted with a linear, branched or cyclic alkyl group.

  Further, one or more hydrogen atoms in the alkyl group may be optionally substituted with a halogen atom. Examples of the halogen atom substituted for the hydrogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

  In the general formula (2), the alkylene group represented by D may be linear, branched or cyclic. When the alkylene group is cyclic, it may be monocyclic or polycyclic.

  Examples of the linear or branched alkylene group include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-hexylene group, an n-heptylene group, an n-octylene group, and an n-dodecylene group. Etc.

  One or more hydrogen atoms in the alkylene group may be optionally substituted with a halogen atom. Examples of the halogen atom substituted for the hydrogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

  In the above general formula (2), the alkynyl group represented by D may be linear, branched or cyclic. When the alkynyl group is cyclic, it may be monocyclic or polycyclic.

  Examples of the linear or branched alkynyl group include ethynyl group, 2-propynyl group (propargyl group) and the like.

  One or more hydrogen atoms in the alkynyl group may be optionally substituted with a halogen atom. Examples of the halogen atom substituted for the hydrogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

When the photosensitizing ligand represented by the general formula (2) has an alkyl group as R ¹ , R ² and D, solubility in the solvent is improved by selecting an appropriate solvent. By using a photosensitizing ligand having high solubility in a solvent, the handling property of the binuclear complex is further improved. For example, a light-emitting element described later can easily obtain a light-emitting element.

(Wherein, ^{R 3} and ^{R 4} are each _{independently} a C n _H hydrocarbon group represented by _m, C n _{H m} have been substituted by hydrocarbon H to another element represented by X X represents a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a selenium atom, or a phosphorus atom.)

In the general formula (3), is a ^{group R 3} and ^{R 4} is substituted with _C n _{H m} hydrocarbon group or represented by _C n _{H m} X _H from hydrocarbon represented by the other elements , group substituted by a hydrocarbon H to another element represented by C _n H hydrocarbon group or a C _n represented by _{m H} m _X, for example, an alkyl group, an alkylene group, an alkynyl group, an aryl group, Heteroaryl group etc. are mentioned.
The alkyl group may be linear, branched or cyclic. When the alkyl group is cyclic, it may be monocyclic or polycyclic.

  Examples of linear or branched alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, and n-pentyl. Group, isopentyl group, neopentyl group, tert-pentyl group, 1-methylbutyl group, n-hexyl group, 2-methylpentyl group, 3-methylpentyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group N-heptyl group, 2-methylhexyl group, 3-methylhexyl group, 2,2-dimethylpentyl group, 2,3-dimethylpentyl group, 2,4-dimethylpentyl group, 3,3-dimethylpentyl group, 3-ethylpentyl group, 2,2,3-trimethylbutyl group, n-octyl group, isooctyl group, nonyl group, decyl group, undecyl group, dodecyl group Group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, heneicosyl group, docosyl group.

  Examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, a norbornyl group, an isobornyl group, a 1-adamantyl group, and a 2-adamantyl group. Group, tricyclodecyl group and the like. Furthermore, examples of the alkyl group include those in which one or more hydrogen atoms of these cyclic alkyl groups are substituted with a linear, branched or cyclic alkyl group.

  Further, one or more hydrogen atoms in the alkyl group may be optionally substituted with a halogen atom. Examples of the halogen atom substituted for the hydrogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

In the general formula (3), the alkylene group represented by R ³ and R ⁴ may be linear, branched or cyclic. When the alkylene group is cyclic, it may be monocyclic or polycyclic.

  Examples of the linear or branched alkylene group include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-hexylene group, an n-heptylene group, an n-octylene group, and an n-dodecylene group. Etc.

  One or more hydrogen atoms in the alkylene group may be optionally substituted with a halogen atom. Examples of the halogen atom substituted for the hydrogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

In the general formula (3), the alkynyl group represented by R ³ and R ⁴ may be linear, branched, or cyclic. When the alkynyl group is cyclic, it may be monocyclic or polycyclic.

  Examples of the linear or branched alkynyl group include ethynyl group, 2-propynyl group (propargyl group) and the like.

  One or more hydrogen atoms in the alkynyl group may be optionally substituted with a halogen atom. Examples of the halogen atom substituted for the hydrogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

In the general formula (3), the aryl group represented by R ³ and R ⁴ may be monocyclic or polycyclic.

Examples of the aryl group include a phenyl group, 1-naphthyl group, 2-naphthyl group, o-tolyl group, m-tolyl group, p-tolyl group, xylyl group (dimethylphenyl group) and the like. Further, one or more hydrogen atoms of these aryl groups may be further substituted with these aryl groups or the above alkyl groups represented by R ³ and R ⁴ .

In the general formula (3), as the heteroaryl group represented by R ³ and R ^4, of the aryl group represented by R ³ and R ^4, 1 or more carbon atoms constituting the aromatic ring skeleton, or In the group in which the carbon atom is substituted with a heteroatom together with a hydrogen atom bonded thereto and has aromaticity, and in the cyclic alkyl group in R ³ and R ⁴ , one or more carbon atoms Together with one or more carbon atoms constituting a ring skeleton, or a hydrogen atom with which the carbon atom is bonded to the single bond (C—C) of And a group substituted with a heteroatom and having aromaticity.
Preferred examples of the hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom, a selenium atom, and a phosphorus atom. The number of heteroatoms constituting the aromatic ring skeleton is not particularly limited, but is preferably 1 to 2. When the number of heteroatoms constituting the aromatic ring skeleton is 2 or more, the plurality of heteroatoms may be all the same, all different, or only partly the same. May be.

When the photosensitizing ligand represented by the general formula (3) has an alkyl group as R ³ and R ⁴ , the solubility in the solvent is improved by selecting an appropriate solvent. By using a photosensitizing ligand having high solubility in a solvent, the handling property of the binuclear complex is further improved. For example, a light-emitting element described later can easily obtain a light-emitting element.

(Wherein, ^{R 5} and ^{R 6} are each _{independently} a C n _H hydrocarbon group represented by _m, C n _{H m} have been substituted by hydrocarbon H to another element represented by X X ¹ and X ² each independently represent a group IVb atom excluding carbon, a group Vb atom excluding nitrogen, and a group VIb atom excluding oxygen, and Y represents a halogen atom, oxygen atom, nitrogen atom, sulfur An atom, a selenium atom, or a phosphorus atom, and a and b each independently represent 0 or 1.)

In the general formula (4), is a ^{group R 5} and ^{R 6} is substituted with _C n _{H m} hydrocarbon group or represented by _C n _{H m} X _H from hydrocarbon represented by the other elements , group substituted by a hydrocarbon H to another element represented by C _n H hydrocarbon group or a C _n represented by _{m H} m _X, for example, an alkyl group, an alkylene group, an alkynyl group, an aryl group, Heteroaryl group etc. are mentioned.
The alkyl group may be linear, branched or cyclic. When the alkyl group is cyclic, it may be monocyclic or polycyclic.

  Examples of linear or branched alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, and n-pentyl. Group, isopentyl group, neopentyl group, tert-pentyl group, 1-methylbutyl group, n-hexyl group, 2-methylpentyl group, 3-methylpentyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group N-heptyl group, 2-methylhexyl group, 3-methylhexyl group, 2,2-dimethylpentyl group, 2,3-dimethylpentyl group, 2,4-dimethylpentyl group, 3,3-dimethylpentyl group, 3-ethylpentyl group, 2,2,3-trimethylbutyl group, n-octyl group, isooctyl group, nonyl group, decyl group, undecyl group, dodecyl group Group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, heneicosyl group, docosyl group.

  Examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, a norbornyl group, an isobornyl group, a 1-adamantyl group, and a 2-adamantyl group. Group, tricyclodecyl group and the like. Furthermore, examples of the alkyl group include those in which one or more hydrogen atoms of these cyclic alkyl groups are substituted with a linear, branched or cyclic alkyl group.

  Further, one or more hydrogen atoms in the alkyl group may be optionally substituted with a halogen atom. Examples of the halogen atom substituted for the hydrogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

In the general formula (4), the alkylene group represented by R ⁵ and R ⁶ may be linear, branched or cyclic. When the alkylene group is cyclic, it may be monocyclic or polycyclic.

  Examples of the linear or branched alkylene group include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-hexylene group, an n-heptylene group, an n-octylene group, and an n-dodecylene group. Etc.

  One or more hydrogen atoms in the alkylene group may be optionally substituted with a halogen atom. Examples of the halogen atom substituted for the hydrogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

In the general formula (4), the alkynyl group represented by R ⁵ and R ⁶ may be linear, branched, or cyclic. When the alkynyl group is cyclic, it may be monocyclic or polycyclic.

  Examples of the linear or branched alkynyl group include ethynyl group, 2-propynyl group (propargyl group) and the like.

  One or more hydrogen atoms in the alkynyl group may be optionally substituted with a halogen atom. Examples of the halogen atom substituted for the hydrogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

In the general formula (4), the aryl group represented by R ⁵ and R ⁶ may be monocyclic or polycyclic.

Examples of the aryl group include a phenyl group, 1-naphthyl group, 2-naphthyl group, o-tolyl group, m-tolyl group, p-tolyl group, xylyl group (dimethylphenyl group) and the like. One or more hydrogen atoms of these aryl groups may be further substituted with these aryl groups or the above alkyl groups represented by R ⁵ and R ⁶ .

In the general formula (4), as the heteroaryl group represented by R ⁵ and R ^6, among the aryl groups represented by R ⁵ and R ^6, 1 or more carbon atoms constituting the aromatic ring skeleton, or In the group in which the carbon atom is substituted with a hetero atom together with the hydrogen atom bonded thereto, and has aromaticity, and in the cyclic alkyl group in R ⁵ and R ⁶ , one or more carbon atoms Together with one or more carbon atoms constituting a ring skeleton, or a hydrogen atom with which the carbon atom is bonded to the single bond (C—C) of And a group substituted with a heteroatom and having aromaticity.
Preferred examples of the hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom, a selenium atom, and a phosphorus atom. The number of heteroatoms constituting the aromatic ring skeleton is not particularly limited, but is preferably 1 to 2. When the number of heteroatoms constituting the aromatic ring skeleton is 2 or more, the plurality of heteroatoms may be all the same, all different, or only partly the same. May be.

When the photosensitizing ligand represented by the general formula (4) has an alkyl group as R ⁵ and R ⁶ , the solubility in the solvent is improved by selecting an appropriate solvent. By using a photosensitizing ligand having high solubility in a solvent, the handling property of the binuclear complex is further improved. For example, a light-emitting element described later can easily obtain a light-emitting element.

In the general formula (4), examples of the group IVb atom excluding carbon represented by X ¹ and X ² include silicon (Si), germanium (Ge), tin (Sn), and lead (Pb).

In the general formula (4), examples of the Vb group atom excluding nitrogen represented by X ¹ and X ² include phosphorus (P), arsenic (As), antimony (Sb), and bismuth (Bi).

In the general formula (4), examples of the group VIb atom excluding oxygen represented by X ¹ and X ² include sulfur (S), selenium (Se), tellurium (Te), and polonium (Po).

(In the formula, R ⁷ represents a hydrocarbon represented by C _n H _m , or a group obtained by substituting H with another element from a hydrocarbon represented by C _n H _m X. X ³ represents carbon. And represents a group IVb atom excluding nitrogen, a group Vb atom excluding nitrogen, and a group VIb atom excluding oxygen, and c represents 0 or 1.)

In the general formula (5), it is a ^{group R 7} is substituted with _C n _H hydrocarbon group or represented by _{m C} n _{H m} X H from hydrocarbon represented by the other elements, _{C n} The hydrocarbon group represented by H _m or the group represented by C _n H _m X substituted with H by another element is, for example, an alkyl group, an alkylene group, an alkynyl group, an aryl group, a heteroaryl group Etc.
The alkyl group may be linear, branched or cyclic. When the alkyl group is cyclic, it may be monocyclic or polycyclic.

  Examples of linear or branched alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, and n-pentyl. Group, isopentyl group, neopentyl group, tert-pentyl group, 1-methylbutyl group, n-hexyl group, 2-methylpentyl group, 3-methylpentyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group N-heptyl group, 2-methylhexyl group, 3-methylhexyl group, 2,2-dimethylpentyl group, 2,3-dimethylpentyl group, 2,4-dimethylpentyl group, 3,3-dimethylpentyl group, 3-ethylpentyl group, 2,2,3-trimethylbutyl group, n-octyl group, isooctyl group, nonyl group, decyl group, undecyl group, dodecyl group Group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, heneicosyl group, docosyl group.

  Examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, a norbornyl group, an isobornyl group, a 1-adamantyl group, and a 2-adamantyl group. Group, tricyclodecyl group and the like. Furthermore, examples of the alkyl group include those in which one or more hydrogen atoms of these cyclic alkyl groups are substituted with a linear, branched or cyclic alkyl group.

  Further, one or more hydrogen atoms in the alkyl group may be optionally substituted with a halogen atom. Examples of the halogen atom substituted for the hydrogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

In the general formula (5), the alkylene group represented by R ⁷ may be linear, branched or cyclic. When the alkylene group is cyclic, it may be monocyclic or polycyclic.

  Examples of the linear or branched alkylene group include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-hexylene group, an n-heptylene group, an n-octylene group, and an n-dodecylene group. Etc.

  One or more hydrogen atoms in the alkylene group may be optionally substituted with a halogen atom. Examples of the halogen atom substituted for the hydrogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

In the general formula (5), the alkynyl group represented by R ⁷ may be linear, branched or cyclic. When the alkynyl group is cyclic, it may be monocyclic or polycyclic.

  Examples of the linear or branched alkynyl group include ethynyl group, 2-propynyl group (propargyl group) and the like.

  One or more hydrogen atoms in the alkynyl group may be optionally substituted with a halogen atom. Examples of the halogen atom substituted for the hydrogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

In the general formula (5), the aryl group represented by R ⁷ may be monocyclic or polycyclic.

Examples of the aryl group include a phenyl group, 1-naphthyl group, 2-naphthyl group, o-tolyl group, m-tolyl group, p-tolyl group, xylyl group (dimethylphenyl group) and the like. One or more hydrogen atoms of these aryl groups may be further substituted with these aryl groups or the above alkyl group represented by R ⁷ .

In the general formula (5), as the heteroaryl group represented by R ^7, of the aryl group represented by R ^7, 1 or more carbon atoms constituting the aromatic ring skeleton, or its carbon atom to In the group substituted with a heteroatom together with a hydrogen atom bonded thereto and having aromaticity and a cyclic alkyl group in R ⁷ , one or more single bonds (C—C) between carbon atoms are One or more carbon atoms that are substituted with a heavy bond (C = C), and further substituted with a heteroatom together with a hydrogen atom that is bonded to the one or more carbon atoms that constitute the ring skeleton, and aromatic Group having a property.
Preferred examples of the hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom, a selenium atom, and a phosphorus atom. The number of heteroatoms constituting the aromatic ring skeleton is not particularly limited, but is preferably 1 to 2. When the number of heteroatoms constituting the aromatic ring skeleton is 2 or more, the plurality of heteroatoms may be all the same, all different, or only partly the same. May be.

When the photosensitizing ligand represented by the general formula (5) has an alkyl group as R ⁷ , the solubility in the solvent is improved by selecting an appropriate solvent. By using a photosensitizing ligand having high solubility in a solvent, the handling property of the binuclear complex is further improved. For example, a light-emitting element described later can easily obtain a light-emitting element.

In the general formula (5), examples of the group IVb atom excluding carbon represented by X ³ include silicon (Si), germanium (Ge), tin (Sn), and lead (Pb).

In the general formula (5), examples of the group Vb atom excluding nitrogen represented by X ³ include phosphorus (P), arsenic (As), antimony (Sb), and bismuth (Bi).

In the general formula (5), examples of the group VIb atom excluding oxygen represented by X ³ include sulfur (S), selenium (Se), tellurium (Te), and polonium (Po).

  The binuclear complex of this embodiment is composed of, for example, a basic skeleton represented by the above general formula (1) and a photosensitizing ligand represented by the above general formula (2). ). That is, in the binuclear complex represented by the following general formula (6), the photosensitizing ligand represented by the above general formula (2) is added to each of the rare earth element cations having the basic skeleton represented by the above general formula (1). Are at least one, usually two or three.

(In the formula, n represents 1, 2 or 3.)

  The binuclear complex of the present embodiment is composed of, for example, a basic skeleton represented by the general formula (1) and a photosensitizing ligand represented by the general formula (3). It is represented by (7). That is, in the binuclear complex represented by the following general formula (7), the photosensitizing ligand represented by the general formula (3) is added to each of the rare earth element cations having the basic skeleton represented by the general formula (1). Are at least one, usually two or three.

(In the formula, n represents 1, 2 or 3.)

  The binuclear complex of the present embodiment is composed of, for example, a basic skeleton represented by the general formula (1) and a photosensitizing ligand represented by the general formula (4). It is represented by (8). That is, in the binuclear complex represented by the following general formula (8), the photosensitizing ligand represented by the general formula (4) is added to each of the rare earth element cations having the basic skeleton represented by the general formula (1). Are at least one, usually two or three.

(In the formula, n represents 1, 2 or 3.)

  The binuclear complex of the present embodiment is composed of, for example, a basic skeleton represented by the above general formula (1) and a photosensitizing ligand represented by the above general formula (5). It is represented by (9). That is, in the binuclear complex represented by the following general formula (9), the photosensitizing ligand represented by the general formula (5) is added to each of the rare earth element cations having the basic skeleton represented by the general formula (1). Are at least one, usually two or three.

(In the formula, n represents 1, 2 or 3.)

In the above general formulas (6) to (9), the ligands coordinated to the rare earth element cations of the first complex structure and the rare earth element cations of the second complex structure constituting the basic skeleton are 1 to 3, respectively. The number of ligands is not particularly limited as long as it is individual and can be spatially coordinated. The cation (rare earth ion) which is A constituting the basic skeleton of the binuclear complex represented by the general formula (1) is often stable at 3 ⁺ (trivalent). In addition, since the carboxylate anion (RCOO ⁻ ) is 1 ⁻ (monovalent), it is considered that two ligands coordinate with each cation and become stable. In addition, some rare earth ions can be 4 ⁺ (tetravalent). In this case, it is considered that three ligands coordinate with each cation and become stable.

  In the general formulas (6) to (9), the same kind of photosensitizing ligand is present on each of the rare-earth element cation having the first complex structure and the rare-earth element cation having the second complex structure constituting the basic skeleton. The case where one, two, or three coordination bonds are illustrated, but the present embodiment is not limited to this. In the present embodiment, for example, one or two photosensitizing ligands represented by the general formulas (2) to (5) are included in the rare earth element cation of the rare earth element cation having the first complex structure. Three coordinate bonds may be formed, and water molecules may be coordinated as ligands to the rare earth element cations of the second complex structure, and the photosensitizing distributions represented by the above general formulas (2) to (5) may be used. In addition to the ligand, water molecules and anions represented by the following formulas (11) to (18) may be coordinated as ligands.

The emission mechanism of trivalent rare earth ions originates from the transition between f orbitals (f-f transition). Originally, this ff transition is a transition having a very low luminous efficiency called a forbidden transition. However, the forbidden transition, which is a forbidden transition, is also disrupted by the arrangement of anions (ligands) around the rare earth ions, and the ff transition is allowed (emission efficiency is increased. Luminance of light emission). Increase).
Generally, the luminous efficiency of rare earth ions can be increased by the coordination of anions as shown in the following formulas (11) to (18) around the rare earth ions.

As the binuclear complex of this embodiment, specifically, as shown in FIG. 2, in the general formula (6), R is a methyl group (—CH ₃ ), A is a europium ion (Eu ³⁺ ), R ¹ and R ² are CF ₃ and D is hydrogen. That is, in the binuclear complex of this example, the photosensitizing ligand represented by the general formula (2) is an anion of hexafluoroacetylacetone (C ₅ O ₂ HF ₆ ) represented by the following formula (10) ( (C ₅ O ₂ HF ₆ ) ⁻ ).

Moreover, specifically as a binuclear complex of this embodiment, the compound represented by following formula (11) is mentioned. In the following formula (11), a basic skeleton represented by the general formula (1), wherein R is a methyl group (—CH ₃ ), and A is a europium ion (Eu ³⁺ ) is abbreviated as Eu (III). . The compound represented by the following formula (11) includes an anion of 1,1′-biphenyl-2,2′-diylbisdiphenylphosphine oxide (BIPHEPO) on each europium ion (Eu ³⁺ ) of Eu (III), Three anions of hexafluoroacetylacetone (hfa) are coordinated.

Moreover, specifically as a binuclear complex of this embodiment, the compound represented by following formula (12) is mentioned. In the following formula (12), a basic skeleton represented by the above general formula (1), wherein R is a methyl group (—CH ₃ ), and A is a europium ion (Eu ³⁺ ) is abbreviated as Eu (III). . The compound represented by the following formula (12) is obtained by adding two triphenylphosphine oxide (TPPO) anions and three hexafluoroacetylacetone (hfa) to each europium ion (Eu ³⁺ ) of Eu (III). An anion is coordinated to the anion.

Moreover, specifically as a binuclear complex of this embodiment, the compound represented by following formula (13) is mentioned. In the following formula (13), a basic skeleton represented by the above general formula (1), wherein R is a methyl group (—CH ₃ ), and A is a europium ion (Eu ³⁺ ) is abbreviated as Eu (III). . The compound represented by the following formula (13) includes two anions of diphenylphosphine oxide (OPPO) and three hexafluoroacetylacetones (hfa) on each europium ion (Eu ³⁺ ) of Eu (III). An anion is coordinated to the anion.

Moreover, specifically as a binuclear complex of this embodiment, the compound represented by following formula (14) is mentioned. In the following formula (14), a basic skeleton represented by the above general formula (1), wherein R is a methyl group (—CH ₃ ), and A is a europium ion (Eu ³⁺ ) is abbreviated as Eu (III). . The compound represented by the following formula (14) is obtained by combining an europium ion (Eu ³⁺ ) of Eu (III) with an anion of diphenylphosphinopropyldiphenylphosphine oxide (DPPPO) and three hexafluoroacetylacetones (hfa). An anion is coordinated to the anion.

Moreover, specifically as a binuclear complex of this embodiment, the compound represented by following formula (15) is mentioned. In the following formula (15), a basic skeleton represented by the above general formula (1), wherein R is a methyl group (—CH ₃ ), and A is a europium ion (Eu ³⁺ ) is abbreviated as Eu (III). . The compound represented by the following formula (15) includes an anion of {bis [o- (diphenylphosphoryl) phenylyl] phenylphosphine oxide} (DPYPPO) and each of europium ions (Eu ³⁺ ) of Eu (III) and three hexagons. The anion of fluoroacetylacetone (hfa) is coordinated.

Moreover, specifically as a binuclear complex of this embodiment, the compound represented by following formula (16) is mentioned. In the following formula (16), a basic skeleton represented by the above general formula (1), wherein R is a methyl group (—CH ₃ ), and A is a europium ion (Eu ³⁺ ) is abbreviated as Eu (III). . The compound represented by the following formula (16) includes an anion of bis [o- (diphenylphosphoryl) benzothienyl] phenylphosphine oxide (DPBTPO) and three hexafluoroacetylacetones on each europium ion (Eu ³⁺ ) of Eu (III). The anion of (hfa) is coordinated.

Moreover, specifically as a binuclear complex of this embodiment, the compound represented by following formula (17) is mentioned. In the following formula (17), a basic skeleton represented by the above general formula (1), wherein R is a methyl group (—CH ₃ ), and A is a europium ion (Eu ³⁺ ) is abbreviated as Eu (III). . The compound represented by the following formula (17) is obtained by adding two diphenylphosphinodimethylxanthenes (4,5-bis (diphenylphosphoryl) -9,9-dimethylxanthene) to each europium ion (Eu ³⁺ ) of Eu (III). xantpo) anion and three hexafluoroacetylacetone (hfa) anions are coordinated.

Moreover, specifically as a binuclear complex of this embodiment, the compound represented by following formula (18) is mentioned. In the following formula (18), a basic skeleton represented by the above general formula (1), wherein R is a methyl group (—CH ₃ ), and A is a europium ion (Eu ³⁺ ) is abbreviated as Eu (III). . The compound represented by the following formula (18) is obtained by adding di-tert-butylphosphinodimethylxanthene (4,5-bis (di-tert-butylphosphory) -9,9 to each europium ion (Eu ³⁺ ) of Eu (III). The anion of -dimethylxanthene and tBu-xantpo) and the anion of three hexafluoroacetylacetones (hfa) are coordinated.

(Method for producing binuclear complex)
The binuclear complex represented by the general formulas (6) to (9) is manufactured by the following manufacturing method.
A rare earth acetate (for example, europium acetate) is dissolved in pure water to prepare an aqueous solution of the rare earth acetate.
Next, the ligand is added to the aqueous solution of rare earth acetate, and the mixture is stirred at room temperature to 100 ° C. for about 1 hour to 10 hours.
Next, the aqueous solution of the rare earth acetate to which the ligand is added is purified by a crystallization method, a liquid-liquid extraction method, or the like to obtain the binuclear complex represented by the above general formulas (6) to (9).
Furthermore, by recrystallizing the obtained binuclear complex using an organic solvent such as methanol or chloroform, a high purity binuclear complex can be obtained.

  According to the binuclear complex of the present embodiment, the excitation spectrum is broad at a wavelength of 250 nm to 450 nm, and the emission peak wavelength emitted from the blue LED element absorbs light in the blue region of 420 nm to 480 nm to emit light. Light (fluorescence) in the visible light region having a sharp spectrum near the wavelength of 610 nm can be emitted. Therefore, when the binuclear complex of this embodiment is used as a red phosphor of a white LED, there is no loss of light in the deep red region (region longer than 650 nm). A white LED having excellent luminous efficiency can be realized without adjustment.

Second Embodiment (Light Emitting Element)
The light-emitting element of this embodiment includes a semiconductor light-emitting element, a resin surrounding the semiconductor light-emitting element, and a fluorescent light that is dispersed in the resin and excited by light emitted from the semiconductor light-emitting element and has a wavelength different from the excitation wavelength. And at least two phosphors emitting one of the phosphors, wherein one of the phosphors comprises the binuclear complex of the first embodiment described above.

Hereinafter, the light emitting device of this embodiment will be described in detail with reference to FIG. FIG. 3 is a cross-sectional view illustrating a schematic configuration of a white light emitting diode (white LED) 10 as an example of the light emitting element of the present embodiment.
The white LED 10 includes a semiconductor light emitting element 11, a resin 12 surrounding the entire semiconductor light emitting element 11, phosphors 13 and 14 (green phosphor 13 and red phosphor 14) dispersed in the resin 12, and a semiconductor light emitting element. 11, a frame 15 that accommodates the resin 12 and the phosphors 13 and 14, and a lead frame 16 on which the semiconductor light emitting element 11 and the frame 15 are placed.

The frame 15 includes a recess 15b having a reflecting surface 15a. The reflective surface 15a may be provided with a reflective film made of a metal film containing silver or aluminum in order to efficiently extract emitted light.
When a metal film is not provided on the reflecting surface 15a, the frame 15 is made of a material having light reflectivity (for example, a high concentration of titanium oxide in a resin such as nylon resin or silicone resin). It is preferable to have a structure with increased reflectance.
The cross-sectional shape of the concave portion 15 b is an inversely tapered shape in which the cross-sectional shape becomes wider in the direction away from the lead frame 16. That is, the width of the bottom surface 15 c of the recess 15 b is narrower than the opening width on the upper surface 15 d side of the frame body 15.
The frame 15 is formed by insert-molding a pair of lead frames 16A and 16B in a nylon resin material. One end of each of the lead frames 16A and 16B is exposed at the bottom surface 15c of the recess 15b of the frame body 15 and is disposed apart from each other. The other ends of the lead frames 16A and 16B are cut to a predetermined length and are bent along the outer surface 15e of the frame 15 (the outer surface below the recess 15b). It is extended to form an external terminal.

  The semiconductor light emitting element 11 is electrically bonded by bonding the upper electrode (not shown) of the semiconductor light emitting element 11 to one end of the lead frame 16A and one end of the lead frame 16B. As a result, the semiconductor light emitting element 11 is fixed to a predetermined position on the bottom surface 15c of the recess 15b of the frame 15.

The entire semiconductor light emitting element 11 disposed on the bottom surface 15c of the recess 15b of the frame 15, and one end of the lead frames 16A and 16B and the bonding wire 17 disposed in the vicinity thereof are transparent resin filled in the recess 15b. 12 is sealed. Further, in the resin 12, phosphors 13 and 14 and a sedimentation inhibitor 18 for suppressing sedimentation of the phosphors 13 and 14 are dispersed. As the sedimentation-inhibiting material 18, silica fine powder or the like is used.
By dispersing the sedimentation suppression material 18 together with the phosphors 13 and 14, even if the time until the resin 12 is cured varies, the influence of sedimentation of the phosphors 13 and 14 is suppressed. The phosphors 13 and 14 are preferably maintained in a state of being uniformly dispersed in the resin 12. By dispersing the sedimentation suppression material 18 together with the phosphors 13 and 14, it is possible to suppress manufacturing variations and uneven color of emitted light due to the bias of the phosphors 13 and 14.

  The semiconductor light emitting device 11 is a GaN-based semiconductor light emitting device, and two electrodes (an anode electrode and a cathode electrode) are formed on the surface opposite to the bottom surface. The emission peak wavelength of light emission (emitted light) from the semiconductor light emitting element 11 is not less than 380 nm and not more than 470 nm. For example, the emitted light has a peak wavelength at 445 nm in the blue region.

The resin 12 is not particularly limited as long as it transmits light emitted from the semiconductor light emitting element 11, the green phosphor 13, and the red phosphor 14. As the resin 12, a thermoplastic resin, a thermosetting resin, a photocurable resin, or the like is used. Specifically, a methacrylic resin such as polymethyl methacrylate; a styrene resin such as polystyrene or a styrene-acrylonitrile copolymer; Polycarbonate resin; Polyester resin; Phenoxy resin; Butyral resin; Polyvinyl alcohol; Cellulose resin such as ethyl cellulose, cellulose acetate, cellulose acetate butyrate; Epoxy resin; Phenol resin; Addition reaction type silicone resin, condensation reaction type silicone resin, modified silicone Examples thereof include silicone resins such as resins. These resin may be used individually by 1 type, and may be used in combination of 2 or more type.
Among these resins, a silicone resin is preferable because of its high durability against primary light having a short wavelength (light emitted from the semiconductor light emitting element 11).

The green phosphor 13 is not particularly limited as long as it emits green secondary light in the green region having an emission peak wavelength of 500 nm to 550 nm. For example, Eu activated β sialon (Si _{(6-z) al z O z N (8-} z): Eu 2+) is used.

As the red phosphor 14, the binuclear complex of the first embodiment described above is used.
The binuclear complex preferably contains at least Eu, the emission peak wavelength of the binuclear complex is preferably 605 nm or more and 620 nm or less, and the full width at half maximum of the emission peak of the binuclear complex is preferably 15 nm or less.
The binuclear complex preferably contains at least Tb, the emission peak wavelength of the binuclear complex is 535 nm or more and 550 nm or less, and the full width at half maximum of the emission peak of the binuclear complex is preferably 15 nm or less.
The binuclear complex preferably contains at least Sm, the emission peak wavelength of the binuclear complex is 635 nm or more and 650 nm or less, and the full width at half maximum of the emission peak of the binuclear complex is preferably 15 nm or less.

Depending on the purpose of the white LED 10, the emission spectrum can be adjusted by mixing the green phosphor 13 and the red phosphor 14 with another phosphor.
When the white LED 10 is used as illumination, an emission spectrum with good color rendering properties can be obtained. When the white LED 10 is used as a backlight, the color reproduction range (color gamut) can be expanded. The “combination of phosphor 13 and red phosphor 14” is frequently used.
Further, “a combination of the semiconductor light emitting element 11, the yellow phosphor, and the red phosphor 14” using a yellow phosphor instead of the green phosphor 13 may be used.

The yellow phosphor is not particularly limited as long as it emits yellow secondary light having an emission peak wavelength in the yellow region near 560 nm. For example, Ce: YAG, BOSE (Ba, Sr, O, Eu) ), Eu activated α sialon or the like is used.
When the yellow phosphor is used, the white LED 10 includes primary light that is emitted from the semiconductor light emitting element 11 (blue light in a blue region having an emission peak wavelength of 420 nm to 480 nm), a yellow phosphor, and a red phosphor. A so-called pseudo-white type white LED that emits combined light with secondary light that is 14 light emission (fluorescence) is obtained. Even a yellow phosphor has a green component and a red component in addition to the yellow component.

In addition to the red phosphor 14, a red phosphor (for example, CaAlSiN 3: Eu ²⁺ ) that emits red secondary light in the red region having an emission peak wavelength of 600 nm to 780 nm can be mixed and used.

  A phosphor is an optical functional material that absorbs ultraviolet light or visible light, emits visible light or infrared light, and emits it. As other phosphors other than the green phosphor 13 and the red phosphor 14, an organic phosphor or an inorganic phosphor is used.

  Organic phosphors include coumarin dyes, perylene dyes, phthalocyanine dyes, stilbene dyes, cyanine dyes, polyphenylene dyes, xanthene dyes, pyridine dyes, oxazine dyes, chrysene dyes, thioflavine dyes, Perylene dye, pyrene dye, anthracene dye, acridone dye, acridine dye, fluorene dye, terphenyl dye, ethene dye, butadiene dye, hexatriene dye, oxazole dye, coumarin dye, Stilbene dyes, diphenylmethane dyes, triphenylmethane dyes, thiazole dyes, thiazine dyes, naphthalimide dyes, anthraquinone dyes and the like are preferably used. Specifically, 3- (2′-benzothiazolyl) -7-diethylaminocoumarin (coumarin 6), 3- (2′-benzoimidazolyl) -7-N, N-diethylaminocoumarin (coumarin 7), 3- (2 ′ -N-methylbenzimidazolyl) -7-N, N-diethylaminocoumarin (coumarin 30), 2,3,5,6-1H, 4H-tetrahydro-8-trifluoromethylquinolidine (9,9a, 1-gh) Coumarin dyes such as coumarin (coumarin 153), naphthalimide dyes such as basic yellow 51, solvent yellow 11 and solvent yellow 116, which are coumarin dye dyes, rhodamine B, rhodamine 6G, rhodamine 3B, rhodamine 101, rhodamine 110, Sulforhodamine, basic violet 11, basic Rhodamine dyes such as red 2, pyridine dyes such as 1-ethyl-2- [4- (p-dimethylaminophenyl) -1,3-butadienyl] pyridinium-perchlorate (pyridine 1), cyanine dyes, oxazines A system dye or the like is used.

  The inorganic phosphor may be subjected to a surface modification treatment as necessary. The method may be a chemical treatment such as a silane coupling agent or a physical treatment by adding particles of submicron order. And those obtained by a combination thereof. In consideration of stability such as deterioration due to excitation light and light emission, it is generally preferable to use an inorganic phosphor.

Among the inorganic phosphors, metal oxides represented by Y ₂ O ₃ and Zn ₂ SiO ₄ which are crystal bases, metal nitrides represented by Sr ₂ Si ₅ N _{8 and the} like, Ca ₅ (PO ₄ ) ₃ Phosphate represented by Cl and the like, and sulfides represented by ZnS, SrS, CaS and the like, and rare earths such as Ce, Pr, Nd, Pm, Sm, Eu, Tb, Dy, Ho, Er, Tm, and Yb A combination of metal ions and metal ions such as Ag, Cu, Au, Al, Mn, and Sb as activators or coactivators is preferred.

Preferable specific examples of the crystal matrix include sulfides such as (Zn, Cd) S, SrGa ₂ S ₄ , SrS, CaS, and ZnS, oxysulfides such as Y ₂ O ₂ S, and (Y, Gd) _3. Al ₅ O ₁₂ , YAlO ₃ , BaMgAl ₁₀ O ₁₇ , (Ba, Sr) (Mg, Mn) Al ₁₀ O ₁₇ , (Ba, Sr, Ca) (Mg, Zn, Mn) Al ₁₀ O ₁₇ , BaAl ₁₂ O ₁₉ , CeMgAl ₁₁ O ₁₉ , (Ba, Sr, Mg) O · Al ₂ O ₃ , BaAl ₂ Si ₂ O ₈ , SrAl ₂ O ₄ , Sr ₄ Al ₁₄ O ₂₅ , Y ₃ Al ₅ O _12, etc. Salt, silicate such as Y ₂ SiO ₅ and Zn ₂ SiO ₄ , oxide such as SnO ₂ and Y ₂ O ₃ , borate such as GdMgB ₅ O ₁₀ and (Y, Gd) BO ₃ , Ca ₁₀ (PO ₄ ) _{(F, Cl) 2, (} Sr, Ca, Ba, Mg) 10 (PO 4) 6 halophosphate _two such _{Cl, Sr 2 P 2 O 7} , (La, Ce) phosphate PO ₄ 4 etc. , (Mg, Ca, Sr, Ba) ₂ Si ₅ N ₈ , (Mg, Ca, Sr, Ba) AlSiN _{3 and} other metal nitrides.

  However, the elemental composition of the crystal matrix and the activator element or coactivator element is not particularly limited, and it can be partially replaced with an element of the same family, and the obtained inorganic phosphor has a light in the ultraviolet region to the visible region. Any material that absorbs light and emits visible light can be used.

  Specific examples of the inorganic phosphor include the following red inorganic phosphor, green inorganic phosphor, blue inorganic phosphor, and yellow inorganic phosphor. However, these phosphors are merely examples, and the phosphors used in the present embodiment are not limited to these.

Among the inorganic phosphors, the red inorganic phosphor that emits light in the red region is composed of, for example, broken particles having a red fracture surface, and emits light in the red region (Mg, Ca, Sr, Ba) _2. A europium-activated alkaline earth silicon nitride-based phosphor represented by Si ₅ N ₈ : Eu, composed of grown particles having a substantially spherical shape as a regular crystal growth shape, and emits light in the red region (Y, La, Gd, Lu) ₂ O ₂ S: Europium activated rare earth oxychalcogenide phosphors represented by Eu.

  In addition, as the red inorganic phosphor, for example, at least one element selected from the group consisting of Ti, Zr, Hf, Nb, Ta, W and Mo described in JP-A-2004-300247 is used. A phosphor containing at least one of an oxynitride and an oxysulfide containing an oxynitride having an alpha sialon structure in which a part or all of an Al element is substituted with a Ga element Can also be used.

Furthermore, examples of the red inorganic phosphor include Eu-activated oxysulfide phosphors such as (La, Y) ₂ O ₂ S: Eu, Y (V, P) O ₄ : Eu, and Y ₂ O ₃ : Eu. Eu activated oxide phosphor such as (Ba, Sr, Ca, Mg) ₂ SiO ₄ : Eu, Mn, (Ba, Mg) ₂ SiO ₄ : Eu, Mn activated silicate phosphor such as Eu, Mn Eu-activated tungstate fluorescence such as LiW ₂ O ₈ : Eu, LiW ₂ O ₈ : Eu, Sm, Eu ₂ W ₂ O ₉ , Eu ₂ W ₂ O ₉ : Nb, Eu ₂ W ₂ O ₉ : Sm Bodies, Eu-activated sulfide phosphors such as (Ca, Sr) S: Eu, Eu-activated aluminate phosphors such as YAlO ₃ : Eu, LiY ₉ (SiO ₄ ) ₆ O ₂ : Eu, Ca ₂ Y _{8 (SiO 4) 6 O 2} : Eu, (Sr, Ba, Ca) 3 SiO 5: Eu, r ₂ BaSiO _5: Eu-activated silicate phosphors such as _{Eu, (Y, Gd) 3} Al 5 O 12: Ce, (Tb, Gd) 3 Al 5 O 12: Ce -activated aluminate phosphor such as Ce Eu-activated nitriding such as (Ca, Sr, Ba) ₂ Si ₅ N ₈ : Eu, (Mg, Ca, Sr, Ba) SiN ₂ : Eu, (Mg, Ca, Sr, Ba) AlSiN ₃ : Eu Phosphors, Ce-activated nitride phosphors such as (Mg, Ca, Sr, Ba) AlSiN ₃ : Ce, (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu, Mn, etc. Eu, Mn activated halophosphate phosphor, (Ba ₃ Mg) Si ₂ O ₈ : Eu, Mn, (Ba, Sr, Ca, Mg) ₃ (Zn, Mg) Si ₂ O ₈ : Eu, Mn, etc. eu, Mn-activated silicate phosphors, 3.5MgO · 0.5MgF ₂ · eO _2: Mn activated germanate salt phosphors such as Mn, Eu Tsukekatsusan nitride phosphor such as Eu-activated _{α-sialon, (Gd, Y, Lu,} La) 2 O 3: Eu, Eu Bi, etc. , Bi activated oxide phosphor, (Gd, Y, Lu, La) ₂ O ₂ S: Eu, Bi activated oxysulfide phosphor such as Eu, Bi, (Gd, Y, Lu, La) VO4: Eu, Bi activated vanadate phosphors such as Eu, Bi, etc., SrY ₂ S ₄ : Eu, Ce activated sulfide phosphors such as Eu, Ce, etc., Ce activated sulfide fluorescence such as CaLa ₂ S ₄ : Ce, etc. (Ba, Sr, Ca) MgP ₂ O ₇ : Eu, Mn, (Sr, Ca, Ba, Mg, Zn) ₂ P ₂ O ₇ : Eu, Mn-activated phosphate phosphors such as Eu and Mn _{, (Y, Lu) 2 WO} 6: Eu, Eu such as Mo, Mo-activated tungstate phosphor, (Ba, Sr _{Ca) x Si y N z:} Eu, Ce ( provided that, x, y, z are an integer of 1 or more), such as Eu, Ce-activated nitride _{phosphor, (Ca, Sr, Ba,} Mg) 10 (PO _{4) 6 (F, Cl,} Br, OH): Eu, Eu such as Mn, Mn-activated halophosphate _{phosphor, ((Y, Lu, Gd} , Tb) 1-x Sc x Ce y) 2 (Ca , Mg) _1-r (Mg, Zn) _{2 + r} Si _z-q Ge _q O _{12 + δ,} etc. Ce-activated silicate phosphor, (Sr, Mg) ₃ (PO ₄ ) ₂ : Sn-activated phosphoric acid of Sn ²⁺ It is also possible to use a salt phosphor or the like.

Further, Y ₂ O ₂ S: Eu ³⁺ , YAlO ₃ : Eu ³⁺ , Ca ₂ Y ₂ (SiO ₄ ) ₆ : Eu ³⁺ , LiY ₉ (SiO ₄ ) ₆ O ₂ : Eu ³⁺ , YVO ₄ : Eu ³⁺ , CaS : Eu ³⁺ , Gd ₂ O ₃ : Eu ³⁺ , Gd ₂ O ₂ S: Eu ³⁺ , Y (P, V) O ₄ : Eu ³⁺ , Mg ₄ GeO _5.5 F: Mn ⁴⁺ , Mg ₄ GeO ₆ : Mn ⁴⁺ , K ₅ Eu _2.5 (WO ₄ ) _6.25 , Na ₅ Eu _2.5 (WO ₄ ) _6.25 , K ₅ Eu _2.5 (MoO ₄ ) _6.25 , Na ₅ Eu _2.5 (MoO ₄ ) _6.25 , (Sr, Ca) AlSiN ₃ : Eu ²⁺ , CaAlSiN ₃ : Eu ²⁺ , SrSiN ₂ : Eu ²⁺ , SrAlSiN ₃ : Eu ²⁺ , Ca ₂ Si ₅ N ₈ : Eu ²⁺ , Sr ₂ Si ₅ N ₈ : Eu ²⁺ , Ba ₂ AlSi ₅ N ₈ : Eu ²⁺ , Sr ₂ Si ₃ O ₂ N ₄ : Eu ²⁺ , Sr ₂ Si ₃ Al ₂ O ₂ N ₆ : Eu ²⁺ , SrSc ₂ O ₄ : Eu ²⁺ , (Sr, Ba) ₃ SiO ₅ : Eu ²⁺ , Mg ₂ TiO ₄ : Mn ^{2+ and the} like.

Among the red inorganic phosphors, those having an emission peak wavelength in the range of 580 nm to 620 nm, preferably 590 nm to 610 nm can be suitably used as the orange inorganic phosphor. Examples of such an orange inorganic phosphor include (Sr, Ba) ₃ SiO ₅ : Eu, (Sr, Mg) ₃ (PO ₄ ) ₂ : Sn ^{2+, and the} like.

Among the inorganic phosphors, the green inorganic phosphor that emits light in the green region includes, for example, broken particles having a green fracture surface, and emits light in the green region (Mg, Ca, Sr, Ba) Si. Europium-activated alkaline earth silicon oxynitride phosphor represented by ₂ O ₂ N ₂ : Eu, composed of fractured particles having a green fracture surface, and emits light in the green region (Ba, Ca, Sr, Mg) ) ₂ SiO ₄ : Europium-activated alkaline earth silicate phosphor represented by Eu.

Examples of the green inorganic phosphor include Eu-activated aluminate phosphors such as Sr ₄ Al ₁₄ O ₂₅ : Eu and (Ba, Sr, Ca) Al ₂ O ₄ : Eu, and (Sr, Ba) Al. _{2 Si 2 O 8: Eu,} (Ba, Mg) 2 SiO 4: Eu, (Ba, Sr, Ca, Mg) 2 SiO 4: Eu, (Ba, Sr, Ca) 2 (Mg, Zn) Si 2 O ₇ : Eu, (Ba, Ca, Sr, Mg) ₉ (Sc, Y, Lu, Gd) ₂ (Si, Ge) ₆ O ₂₄ : Eu-activated silicate phosphor such as Eu, Y ₂ SiO ₅ : Ce Ce, Tb activated silicate phosphor such as Tb, Tb, Sr ₂ P ₂ O ₇ —Sr ₂ B ₂ O ₅ : Eu activated borate phosphate phosphor such as Eu, Sr ₂ Si ₃ O ₈ -2SrCl ₂ : Eu-activated halo silicate phosphor such as _Eu, Zn 2 _SiO 4: Mn, etc. Mn-activated silicate _{phosphor, CeMgAl 11 O 19: Tb,} Y 3 Al 5 O1 2: Tb -activated aluminate phosphor such as _{Tb, Ca 2 Y 8 (SiO} 4) 6 O 2: Tb, La 3 Ga ₅ SiO ₁₄ : Tb-activated silicate phosphor such as Tb, (Sr, Ba, Ca) Ga ₂ S ₄ : Eu, Tb, Sm-activated thiogallate phosphor such as Eu, Tb, Sm, Y ₃ (Al , Ga) ₅ O ₁₂ : Ce, (Y, Ga, Tb, La, Sm, Pr, Lu) ₃ (Al, Ga) ₅ O ₁₂ : Ce-activated aluminate phosphor such as Ce, Ca ₃ Sc ₂ Si ₃ O ₁₂ : Ce, Ca ₃ (Sc, Mg, Na, Li) ₂ Si ₃ O ₁₂ : Ce activated silicate phosphor such as Ce, Ce activated oxide phosphor such as CaSc ₂ O ₄ : Ce _{, SrSi 2 O 2 N 2:} Eu, (Sr, Ba _{Ca) Si 2 O 2 N 2} : Eu, Eu Tsukekatsusan nitride phosphor such as sialon Eu-activated β-sialon, Eu-activated _{α, BaMgAl 10 O 17: Eu} , such as Mn Eu, Mn-activated aluminate Salt phosphor, Eu-activated aluminate phosphor such as SrAl ₂ O ₄ : Eu, Tb-activated oxysulfide phosphor such as (La, Gd, Y) ₂ O ₂ S: Tb, LaPO ₄ : Ce, Ce, Tb-activated phosphate phosphor such as Tb, sulfide phosphor such as ZnS: Cu, Al, ZnS: Cu, Au, Al, (Y, Ga, Lu, Sc, La) BO ₃ : Ce, Tb, Na ₂ Gd ₂ B ₂ O ₇ : Ce, Tb, (Ba, Sr) ₂ (Ca, Mg, Zn) B ₂ O ₆ : Ce, Tb-activated borate phosphor such as K, Ce, Tb, Ca ₈ Mg (SiO ₄ ) ₄ Cl ₂ : Eu, Mn activated materials such as Eu and Mn Borosilicate phosphor, (Sr, Ca, Ba) (Al, Ga, In) ₂ S ₄ : Eu-activated thioaluminate phosphor such as Eu, thiogallate phosphor, (Ca, Sr) ₈ (Mg, Zn) ) (SiO ₄ ) ₄ Cl ₂ : Eu, Mn-activated halosilicate phosphors such as Eu and Mn can also be used.

Furthermore, (BaMg) Al ₁₆ O ₂₇ : Eu ²⁺ , Mn ²⁺ , Sr ₄ Al ₁₄ O ₂₅ : Eu ²⁺ , (SrBa) Al ₁₂ Si ₂ O ₈ : Eu ²⁺ , (BaMg) ₂ SiO ₄ : Eu ²⁺ , Y ^{_{2 SiO 5: Ce 3+, Tb}} 3+, Sr 2 P 2 O 7- Sr 2 B 2 O 5: Eu 2+, (BaCaMg) 5 (PO 4) 3 Cl: Eu 2+, Sr 2 Si 3 O 8 -2SrCl 2 : Eu ²⁺ , Zr ₂ SiO ₄ , MgAl ₁₁ O ₁₉ : Ce ³⁺ , Tb ³⁺ , Ba ₂ SiO ₄ : Eu ²⁺ , Sr ₂ SiO ₄ : Eu ²⁺ , (BaSr) SiO ₄ : Eu ²⁺ , (Si, Al) _{6 (O, N) 8:} Eu 2+, Ca 3 (Sc, Mg) 2 Si 3 O 12: Ce 3+, SrSi 2 (O, Cl) 2 N 2: Eu 2+ Hitoshigakyo It is.

Among the inorganic phosphors, the blue inorganic phosphor that emits light in the blue region includes, for example, BaMgAl ₁₀ that is composed of growing particles having a substantially hexagonal shape as a regular crystal growth shape and emits light in the blue region. Europium-activated barium magnesium aluminate-based phosphor represented by O ₁₇ : Eu, composed of growth particles having a substantially spherical shape as a regular crystal growth shape, and emits light in the blue region (Ca, Sr, Ba) ) ₅ (PO ₄ ) ₃ Cl: Europium-activated calcium halophosphate phosphor represented by Eu, composed of grown particles having a substantially cubic shape as a regular crystal growth shape, and emits light in the blue region (Ca , Sr, Ba) ₂ B ₅ O ₉ Cl: Europium-activated alkaline earth chloroborate phosphor represented by Eu, fracture Europium activation which is composed of fractured particles having a plane and emits light in a blue region represented by (Sr, Ca, Ba) Al ₂ O ₄ : Eu or (Sr, Ca, Ba) ₄ Al ₁₄ O ₂₅ : Eu Examples include alkaline earth aluminate phosphors.

Examples of blue inorganic phosphors include Sn-activated phosphate phosphors such as Sr ₂ P ₂ O ₇ : Sn, Sr ₄ Al ₁₄ O ₂₅ : Eu, BaMgAl ₁₀ O ₁₇ : Eu, BaAl ₈ O _13. : Eu-activated aluminate phosphor such as Eu, SrGa ₂ S ₄ : Ce, CaGa ₂ S ₄ : Ce-activated thiogallate phosphor such as Ce, (Ba, Sr, Ca) MgAl ₁₀ O ₁₇ : Eu, BaMgAl ₁₀ O ₁₇ : Eu-activated aluminate phosphor such as Eu, Tb, Sm, (Ba, Sr, Ca) MgAl ₁₀ O ₁₇ : Eu, Mn-activated aluminate phosphor such as Eu, Mn, (Sr , Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu, (Ba, Sr, Ca) ₅ (PO ₄ ) ₃ (Cl, F, Br, OH): with Eu such as Eu, Mn, Sb Active halolin _{Phosphor, BaAl 2 Si 2 O 8:} Eu, (Sr, Ba) 3 MgSi 2 O 8: Eu -activated silicate phosphors such as _{Eu, Sr 2 P 2 O 7} : Eu -activated phosphate such as Eu Salt phosphors, sulfide phosphors such as ZnS: Ag, ZnS: Ag, Al, Ce activated silicate phosphors such as Y ₂ SiO ₅ : Ce, tungstate phosphors such as CaWO ₄ , (Ba, Sr) , Ca) BPO ₅ : Eu, Mn, (Sr, Ca) ₁₀ (PO ₄ ) ₆ · nB ₂ O ₃ : Eu, 2SrO · 0.84P ₂ O ₅ · 0.16B ₂ O ₃ : Eu, such as Eu, It is also possible to use a Mn-activated borate phosphate phosphor, a Eu-activated halosilicate phosphor such as Sr ₂ Si ₃ O ₈ · 2SrCl ₂ : Eu, or the like.

Furthermore, Sr ₂ P ₂ O ₇ : Sn ⁴⁺ , Sr ₄ Al ₁₄ O ₂₅ : Eu ²⁺ , BaMgAl ₁₀ O ₁₇ : Eu ²⁺ , SrGa ₂ S ₄ : Ce ³⁺ , CaGa ₂ S ₄ : Ce ³⁺ , (Ba, Sr ^{_{) (Mg, Mn) Al 10}} O 17: Eu 2+, (Sr, Ca, Ba 2, 0 Mg) 10 (PO 4) 6 C l2: Eu 2+, BaAl 2 SiO 8: Eu 2+, Sr 2 P 2 O ₇ : Eu ²⁺ , Sr ₅ (PO ₄ ) ₃ Cl: Eu ²⁺ , (Sr, Ca, Ba) ₅ (PO ₄ ) ₃ Cl: Eu ²⁺ , BaMg ₂ Al ₁₆ O ₂₇ : Eu ²⁺ , (Ba, Ca) ₅ (PO ₄ ) ₃ Cl: Eu ²⁺ , Ba ₃ MgSi ₂ O ₈ : Eu ²⁺ , Sr ₃ MgSi ₂ O ₈ : Eu ^{2+ and the} like.

Among inorganic phosphors, yellow inorganic phosphors that emit light in the yellow region include, for example, various oxide-based, nitride-based, oxynitride-based, sulfide-based, and oxysulfide-based phosphors. Can be mentioned. In particular, RE ₃ M ₅ O ₁₂ : Ce (where RE represents at least one element selected from the group consisting of Y, Tb, Gd, Lu and Sm, and M represents Al, Ga and Sc) And M ₂ M ₃ M ₄ O ₁₂ : Ce (where M ₂ is a divalent metal element, M ₃ is a trivalent metal element, M ₄ Represents a tetravalent metal element.) A garnet phosphor having a garnet structure represented by AE ₂ M ₅ O ₄ : Eu (where AE is composed of Ba, Sr, Ca, Mg and Zn). And at least one element selected from the group, and M ₅ represents at least one of Si and Ge.) An orthosilicate phosphor represented by, for example, oxygen of constituent elements of these phosphors Oxynitrides partially substituted with nitrogen Phosphor, AEAlSiN _3: Ce (here, AE is, Ba, Sr, Ca, represents at least one element selected from the group consisting of Mg and Zn.) Nitride phosphor having CaAlSiN ₃ structures such as And phosphors activated by Ce such as a body.

Examples of the yellow inorganic phosphor include sulfides such as CaGa ₂ S ₄ : Eu, (Ca, Sr) Ga ₂ S ₄ : Eu, and (Ca, Sr) (Ga, Al) ₂ S ₄ : Eu. It is also possible to use a phosphor activated with Eu such as an oxynitride-based phosphor having a SiAlON structure such as Ca _x (Si, Al) ₁₂ (O, N) ₁₆ : Eu.

  Various dyes (direct dyes, acid dyes, basic dyes, disperse dyes, etc.) can also be used as phosphors other than the green phosphor 13 and the red phosphor 14 as long as they have fluorescence.

  In such a white LED 10, when a voltage is applied between the pair of lead frames 16 </ b> A and 16 </ b> B, the semiconductor light emitting element 11 emits light in the blue region (primary light), and the fluorescent light disposed around the semiconductor light emitting element 11. The bodies 13 and 14 absorb part of the light in the blue region and emit fluorescence (secondary light) in the visible light region, so that the emitted light in which the primary light and the secondary light are mixed is almost Designed to be white light.

  According to the light emitting device (white LED 10) of the present embodiment, the semiconductor light emitting device 11, the green phosphor 13, and the red phosphor 14 are provided, and the red phosphor 14 is the same as that of the first embodiment described above. Since the nuclear complex is used, there is no light loss in the deep red region (region longer than 650 nm), and the light emitting device having excellent light emission efficiency without adjusting the emission peak wavelength of the semiconductor light emitting device 11 can do.

[Third Embodiment] (Color Conversion Board)
The color conversion substrate of the present embodiment includes a transparent substrate having light transparency, and a color conversion layer that is provided on one surface of the transparent substrate and is excited by external light to emit light having a wavelength different from the excitation wavelength. The color conversion layer includes the binuclear complex of the first embodiment described above.

Hereinafter, the color conversion substrate of this embodiment will be described in detail with reference to FIG. FIG. 4 is a cross-sectional view showing a schematic configuration of the color conversion substrate 20 of the present embodiment.
The color conversion substrate 20 of the present embodiment includes a transparent substrate 21, a color filter layer 22 provided on one surface 21a of the transparent substrate 21, a color conversion layer 23 provided on the color filter layer 22, and a color A partition wall 24 that partitions a pixel (a red pixel 31, a green pixel 32, and a blue pixel 33) including the filter layer 22 and the color conversion layer 23 is schematically configured.

  Of the color filter layer 22, a region constituting the red pixel 31 is a red color filter layer 41. In the color filter layer 22, the region constituting the green pixel 32 is the green color filter layer 42. In the color filter layer 22, a region constituting the blue pixel 33 is a blue color filter layer 43.

Of the color conversion layer 23, a region constituting the red pixel 31 is a red color conversion layer 51. In the color conversion layer 23, a region constituting the green pixel 32 is a green color conversion layer 52. The color conversion layer 23 includes a blue color conversion layer 53 that constitutes the blue pixel 33.
The color conversion layer 23 absorbs near-ultraviolet light, blue light, blue-green light, or white light serving as an excitation light source, and performs wavelength distribution conversion to emit light in the visible light range.

The transparent substrate 21 is a substrate that emits light emitted from an excitation light source, which will be described later, and needs to have light transmittance. Examples of the transparent substrate 21 include an inorganic material substrate made of glass, quartz or the like, a transparent plastic substrate made of polyethylene terephthalate, polycarbazole, polyimide, or the like, but is not limited to these substrates.
Specific examples of the transparent substrate 21 include a glass substrate having a thickness of 0.7 mm, which is generally used for a liquid crystal display or the like.

Moreover, when it is necessary to form a curved part and a bending part in the color conversion board | substrate 20, it is preferable to use said plastic substrate as the transparent substrate 21. FIG.
Further, when it is necessary to improve the gas barrier property, it is more preferable to use a substrate obtained by coating a plastic substrate with an inorganic material as the transparent substrate 21. Thereby, deterioration of the wavelength conversion material due to moisture permeation, which is the biggest problem when a plastic substrate is used as the transparent substrate 21, can be prevented.

  The red color filter layer 41, the green color filter layer 42, and the blue color filter layer 43 absorb excitation light (light emitted from an excitation light source) that excites each phosphor included in the color conversion layer 23 among external light. Further, the light emission of the color conversion layer 23 due to external light can be reduced / prevented, and the decrease in display contrast due to the color conversion substrate 20 can be reduced / prevented. On the other hand, the red color filter layer 41, the green color filter layer 42, and the blue color filter layer 43 can prevent the excitation light that is not absorbed by the color conversion layer 23 and transmitted through the color conversion layer 23 from leaking to the outside. It is possible to prevent a decrease in the color purity of the light emission due to the color mixture of the light emission from the color conversion layer 23 and the excitation light.

Examples of the red color filter layer 41, the green color filter layer 42, and the blue color filter layer 43 include those composed of dyes, pigments, and resins, or those composed only of dyes and pigments.
Examples of the color filter layer composed of a dye, a pigment and a resin include those in a solid state in which a dye and a pigment are dissolved or dispersed in a binder resin.
Examples of the dye and pigment used in the color filter layer include perylene, isoindoline, cyanine, azo, oxazine, phthalocyanine, quinacridone, anthraquinone, and diketopyrrolopyrrole.

The color conversion layer 23 (the red color conversion layer 51, the green color conversion layer 52, and the blue color conversion layer 53) is formed by dispersing phosphors, and may be composed of only phosphor materials. It may be configured to contain additives and the like, and these materials may be configured to be dispersed in a polymer material (transparent resin) or an inorganic material.
Further, the partition wall 24 may not be formed between the red color conversion layer 51, the green color conversion layer 52, and the blue color conversion layer 53, but the red color conversion layer 51 and the green color conversion layer 52 are not necessarily formed. In order to prevent light emission from the blue color conversion layer 53 from being mixed, it is preferable that the partition wall 24 is formed.

The red color conversion layer 51 includes light in an ultraviolet wavelength region (ultraviolet light), blue light among excitation light in an ultraviolet wavelength region to a blue-green wavelength region (hereinafter also simply referred to as “excitation light”). The light in the wavelength range of green and the light in the wavelength range of green are absorbed, and the light in the wavelength range of red is emitted.
The green color conversion layer 52 absorbs light in the ultraviolet wavelength region (ultraviolet light) and blue light in the excitation light, and emits light in the green wavelength region.
The blue color conversion layer 53 absorbs light in the ultraviolet wavelength region (ultraviolet light) in the excitation light, and emits light in the blue wavelength region.

  In the color conversion substrate 20, light from the excitation light source may be directly used as pixel light. For example, when light in a blue wavelength region is used as excitation light, the light may be directly used as light for the blue pixel 33.

The thickness of the color conversion layer 23 (red color conversion layer 51, green color conversion layer 52, blue color conversion layer 53) is usually 100 nm to 100 μm, but preferably 1 μm to 100 μm.
If the thickness of the color conversion layer 23 (the red color conversion layer 51, the green color conversion layer 52, the blue color conversion layer 53) is less than 100 nm, the light in the blue wavelength range irradiated from the excitation light source. Insufficient absorption of light can cause problems such as a decrease in color conversion efficiency and a decrease in color purity of emitted light due to mixing of blue transmitted light with converted light. Further, in order to increase the absorption amount of light in the blue wavelength region irradiated from the excitation light source and reduce the mixing of the blue transmitted light with the converted light to such an extent that the color purity is not lowered, the thickness of the color conversion layer 23 is reduced. The thickness is preferably 1 μm or more. On the other hand, even if the thickness of the color conversion layer 23 (red color conversion layer 51, green color conversion layer 52, blue color conversion layer 53) exceeds 100 μm, the light in the blue wavelength region irradiated from the excitation light source is thick. Even when the thickness is 100 μm or less (100 nm or more), the color conversion efficiency is not increased because it is sufficiently absorbed. Therefore, the material is merely consumed, leading to an increase in material cost.

  As a phosphor material for forming the red color conversion layer 51, the green color conversion layer 52, and the blue color conversion layer 53, a known phosphor material can be used. Such phosphor materials are classified into organic phosphor materials and inorganic phosphor materials.

Organic phosphor materials used for the red phosphor include cyanine dyes such as 4-dicyanomethylene-2-methyl-6- (p-dimethylaminostyryl) -4H-pyran (DCM), 1- Pyridine dyes such as ethyl-2- [4- (p-dimethylaminophenyl) -1,3-butadienyl] -pyridinium-perchlorate, rhodamine B, rhodamine 6G, rhodamine 3B, rhodamine 101, rhodamine 110, basic Examples include rhodamine dyes such as violet 11, sulforhodamine 101, and oxazine dyes.
Examples of inorganic phosphor materials used for the red phosphor include Y ₂ O ₂ S: Eu ³⁺ , YAlO ₃ : Eu ³⁺ , Ca ₂ Y ₂ (SiO ₄ ) ₆ : Eu ³⁺ , LiY ₉ (SiO ₄ ) ₆ O. ₂ : Eu ³⁺ , YVO ₄ : Eu ³⁺ , CaS: Eu ³⁺ , Gd ₂ O ₃ : Eu ³⁺ , Gd ₂ O ₂ S: Eu ³⁺ , Y (P, V) O ₄ : Eu ³⁺ , Mg ₄ GeO _{5. 5} F: Mn ⁴⁺ , Mg ₄ GeO ₆ : Mn ⁴⁺ , K ₅ Eu _2.5 (WO ₄ ) _6.25 , Na ₅ Eu _2.5 (WO ₄ ) _6.25 , K ₅ Eu _2.5 (MoO ₄ ) _6.25 , Na ₅ Eu _2.5 (MoO ₄ ) _{6.25, and the} like.
The red phosphor includes the binuclear complex of the first embodiment described above.

  As the green phosphor, the binuclear complex of the first embodiment described above is used.

In the color conversion substrate of the present embodiment, the binuclear complex includes at least Eu, the emission peak wavelength of the binuclear complex is 605 nm or more and 620 nm or less, and the full width at half maximum of the emission peak of the binuclear complex is 15 nm or less. preferable.
The binuclear complex preferably contains at least Tb, the emission peak wavelength of the binuclear complex is 535 nm or more and 550 nm or less, and the full width at half maximum of the emission peak of the binuclear complex is preferably 15 nm or less.
The binuclear complex preferably contains at least Sm, the emission peak wavelength of the binuclear complex is 635 nm or more and 650 nm or less, and the full width at half maximum of the emission peak of the binuclear complex is preferably 15 nm or less.

Examples of organic phosphor materials used for blue phosphors include stilbene dyes such as 1,4-bis (2-methylstyryl) benzene (Bis-MSB), trans-4,4′-diphenylstilbene (DPS), Examples thereof include coumarin dyes such as 7-hydroxy-4-methylcoumarin (coumarin 4), BOQP, PBBO, BOT, and POPOP.
Examples of the inorganic phosphor material used for the blue phosphor include BaMg ₂ Al ₁₆ O ₂₇ : Eu ²⁺ , Sr ₂ P ₂ O ₇ : Sn ⁴⁺ , Sr ₄ Al ₁₄ O ₂₅ : Eu ²⁺ , BaMgAl ₁₀ O ₁₇ : Eu ²⁺ , SrGa ₂ S ₄ : Ce ³⁺ , CaGa ₂ S ₄ : Ce ³⁺ , (Ba, Sr) (Mg, Mn) Al ₁₀ O ₁₇ : Eu ²⁺ , (Sr, Ca, Ba ₂ , Mg) ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu ²⁺ , BaAl ₂ SiO ₈ : Eu ²⁺ , Sr ₂ P ₂ O ₇ : Eu ²⁺ , Sr ₅ (PO ₄ ) ₃ Cl: Eu ²⁺ , (Sr, Ca, Ba) ₅ (PO ₄ ) ^{_{3 Cl: Eu 2+, (Ba}} , Ca) 5 (PO 4) 3 Cl: Eu 2+, Ba 3 MgSi 2 O 8: Eu 2+, Sr 3 MgSi 2 O 8: Eu 2+ or the like can be mentioned It is.

The polymer material (transparent resin) constituting the color conversion layer 23 preferably has a transmittance of 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region.
The transparent resin includes a thermoplastic resin, a thermosetting resin, and a photosensitive resin. Moreover, the precursor of these transparent resins contains the reactive monomer or reactive oligomer which hardens | cures by irradiation and produces | generates transparent resin. These reactive monomers or reactive oligomers are used alone or in combination of two or more.

  The polymer material (transparent resin) constituting the color conversion layer 23 is composed of a reactive monomer or a reactive oligomer and a photopolymerization initiator having a light absorption region in transmitted light.

(Reactive monomer, Reactive oligomer)
The reactive monomer and the reactive oligomer mean a monomer and an oligomer whose polymerization is induced by a radical generated by the photopolymerization initiator described later absorbing light, and in the present invention, a monomer having the property and Any monomer or oligomer can be used as long as it is an oligomer. As the reactive monomer and reactive oligomer, a compound having at least one polymerizable carbon-carbon unsaturated bond can be used. Examples of reactive monomers and reactive oligomers include acrylic acid, methacrylic acid, polyvinyl cinnamate, fluorene, cycloolefin, imide, silicone, organic / inorganic hybrid, polycarbonate, and TAC. A photocurable material having a reactive vinyl group such as polystyrene, fluorine, polyethylene terephthalate, MS, polyvinyl alcohol, poval, alkyd, or ring rubber is used.

  Specific examples of reactive monomers and reactive oligomers include allyl acrylate, benzyl acrylate, butoxyethyl acrylate, butoxyethylene glycol acrylate, cyclohexyl acrylate, dicyclopentanyl acrylate, 2-ethylhexyl acrylate, glycerol acrylate, glycidyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isobornyl acrylate, isodexyl acrylate, isooctyl acrylate, lauryl acrylate, 2-methoxyethyl acrylate, methoxyethylene glycol acrylate, phenoxyethyl acrylate, stearyl acrylate, ethylene glycol diacrylate Diethylene glycol diacryl 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,3-propanediol acrylate, 1,4-cyclohexanediol diacrylate, 2,2 -Dimethylolpropane diacrylate, glycerol diacrylate, tripropylene glycol diacrylate, glycerol triacrylate, trimethylolpropane triacrylate, polyoxyethylated trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, triethylene glycol Diacrylate, polyoxypropyltrimethylolpropane triacrylate, butylene glycol diacrylate, 1,2, -Butanetriol triacrylate, 2,2,4-trimethyl-1,3-pentanediol diacrylate, diallyl fumarate, 1,10-decanediol dimethyl acrylate, dipentaerythritol hexaacrylate, and methacrylates of the above acrylate groups Substituted with γ-methacryloxypropyltrimethoxysilane, 1-vinyl-2-pyrrolidone, 2-hydroxyethylacryloyl phosphate, tetrahydrofurfryl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, 3- Butanediol diacrylate, neopentyl glycol diacrylate, polyethylene glycol diaclerate, hydroxypivalate ester neopentyl glycol di Chryrate, phenol-ethylene oxide modified acrylate, phenol-propylene oxide modified acrylate, N-vinyl-2-pyrrolidone, bisphenol A-ethylene oxide modified diacrylate, pentaerythritol diacrylate monostearate, tetraethylene glycol diacrylate, polypropylene glycol di Acrylate monomers, such as acrylates, trimethylolpropane propylene oxide modified triacrylate, isocyanuric acid ethylene oxide modified triacrylate, trimethylolpropane ethylene oxide modified triacrylate, pentaerythritol pentaacrylate, pentaerythritol hexaacrylate, pentaerythritol tetraacrylate, and ,these An acrylate group substituted with a methacrylate group, a urethane acrylate oligomer in which an acrylate group is bonded to an oligomer having a polyurethane structure, a polyester acrylate oligomer in which an acrylate group is bonded to an oligomer having a polyester structure, an acrylate group in an oligomer having an epoxy group Bonded epoxy acrylate oligomers, polyurethane methacrylate oligomers with methacrylate groups bonded to polyurethane oligomers, polyester methacrylate oligomers with methacrylate groups bonded to oligomers with polyester structures, and methacrylate groups bonded to oligomers with epoxy groups Epoxy methacrylate oligomer, polyurethane acrylate having acrylate group , Polyester acrylate having an acrylate group, epoxy acrylate resin having an acrylate group, polyurethane methacrylate having a methacrylate group, polyester methacrylate having a methacrylate group, epoxy methacrylate resin having a methacrylate group, and the like.

The above-mentioned reactive monomer and reactive oligomer are examples of the reactive monomer and reactive oligomer that can be used in the present invention, and are not limited thereto.
Moreover, it is preferable that content of such a reactive monomer and reactive oligomer is 10-90 mass% of the non-volatile component of the polymeric material (transparent resin) which comprises the color conversion layer 23, and 20-80 mass % Is more preferable.

A reactive monomer and a reactive oligomer may be used independently and may be used in mixture of 2 or more types.
Among reactive monomers and reactive oligomers, trifunctional or higher polyfunctional acrylate monomers are particularly preferably used.

(Photopolymerization initiator)
The photopolymerization initiator is for generating radicals by absorbing light and initiating the polymerization reaction of the reactive monomer and reactive oligomer.
As the photopolymerization initiator, a radical-generating photopolymerization initiator, an acid-generating photopolymerization initiator, a base-generating photopolymerization initiator, a visible light polymerization initiator, or the like is used.
The acid-generating photopolymerization initiator generates an acid by irradiating ultraviolet rays or the like, and initiates polymerization of a substance having a cationic polymerizable functional group such as a vinyl group or an epoxy group.

  Examples of visible light polymerization initiators include acylphosphine oxide compounds, α-aminoalkylphenone compounds, α-hydroxyalkylphenone compounds, titanocene photopolymerization initiators, hydrogen abstraction type radical photopolymerization initiators, and oxime ester types. Examples include photopolymerization initiators, cationic photopolymerization initiators, and acid generators. Among these visible light polymerization initiators, acylphosphine oxide compounds are particularly preferable.

Examples of the acyl phosphine oxide compound include monoacyl phosphine oxide and bisacyl phosphine oxide.
Specific examples of the acylphosphine oxide compound include benzophenone, Michler's ketone, N, N′tetramethyl-4,4′-diaminobenzophenone, 4-methoxy-4′-dimethylaminobenzophenone, 4,4′-diethylaminobenzophenone, Aromatic ketones such as 2-ethylanthraquinone and phenanthrene, benzoin ethers such as benzoin methyl ether, benzoin ethyl ether and benzoin phenyl ether, benzoins such as methyl benzoin and ethyl benzoin, 2- (o-chlorophenyl) -4,5- Phenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2 -(O-metoki Cyphenyl) -4,5-diphenylimidazole dimer, 2,4,5-triarylimidazole dimer, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2-trichloro Methyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (p-cyanostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (p- Halomethylthiazole compounds such as methoxystyryl) -1,3,4-oxadiazole, 2,4-bis (trichloromethyl) -6-p-methoxystyryl-S-triazine, 2,4-bis (trichloromethyl) -6- (1-p-dimethylaminophenyl-1,3-butadienyl) -S-triazine, 2-trichloromethyl-4-amino-6-p-meth Cistyryl-S-triazine, 2- (naphth-1-yl) -4,6-bis-trichloromethyl-S-triazine, 2- (4-ethoxy-naphth-1-yl) -4,6-bis-trichloro Halomethyl-S-triazine compounds such as methyl-S-triazine, 2- (4-butoxy-naphth-1-yl) -4,6-bis-trichloromethyl-S-triazine, 2,2-dimethoxy-1, 2-diphenylethane-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone, 1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -Butanone-1,1-hydroxy-cyclohexyl-phenyl ketone, Irgacure-369 (manufactured by Ciba Specialty Chemicals), Irgacure-651 (Chi Specialty Chemicals Co., Ltd.), a photopolymerization initiator such as Irgacure -907 (manufactured by Ciba Specialty Chemicals Inc.).
These photopolymerization initiators may be used alone or in combination of two or more.

Examples of the light used for curing the photocurable material include ultraviolet light, visible light, near infrared light, incandescent lamp, fluorescent lamp, and sunlight. Examples of light sources that can irradiate such light include carbon arc lamps, ultra-high pressure mercury lamps, high-pressure mercury lamps, xenon lamps, metal halide lamps, halogen lamps, fluorescent lamps, tungsten lamps, visible light lasers, and light emitting diodes (LEDs). Can be mentioned.
Specific examples of the light source include, for example, light and small semiconductor lasers and LEDs that can irradiate near-ultraviolet light or visible light in a certain region within a radiation wavelength range of 360 to 600 nm.
Examples of the semiconductor laser include a semiconductor violet laser, a semiconductor blue violet laser, and a semiconductor blue laser.
Examples of the LED include a blue LED.
In addition to the above, long-wavelength visible light, infrared, and near-infrared laser irradiators can also be used as light used for curing the photocurable material.
Furthermore, using these light sources, a monochromator, and a cut filter, only light having a specific wavelength may be used.

The light used for curing the photocurable material is light that is incident from the transparent substrate 21 side and transmitted through the color filter layer 22 (red color filter layer 41, green color filter layer 42, blue color filter layer 43). May be used.
At this time, when the photocurable material constituting the red color conversion layer 51 disposed on the red color filter layer 41 is polymerized (cured), the light in the red wavelength region transmitted through the red color filter layer 41 is Used as light for curing the photocurable material.
Further, when the photocurable material constituting the green color conversion layer 52 disposed on the green color filter layer 42 is polymerized (cured), the light in the green wavelength region that has passed through the green color filter layer 42 is converted into light. Used as light for curing the curable material.
Further, when the photocurable material constituting the blue color conversion layer 53 disposed on the blue color filter layer 43 is polymerized (cured), the light in the blue wavelength range transmitted through the blue color filter layer 43 is emitted. Used as light for curing the curable material.

At this time, as the photocurable material constituting the red color conversion layer 51, a material that is polymerized (cured) with light in the red wavelength band that has passed through the red color filter layer 41 is used.
In addition, as the photocurable material constituting the green color conversion layer 52, a material that is polymerized (cured) with light in the green wavelength region that has passed through the green color filter layer 42 is used.
In addition, as the photocurable material constituting the blue color conversion layer 53, a material that is polymerized (cured) with light in the blue wavelength band that has passed through the blue color filter layer 43 is used.

  Examples of the photopolymerization initiator contained in the photocurable material constituting the blue color conversion layer 53 include aromatic ketones, benzoin ethers, benzoins, and imidazole dimers among the above photopolymerization initiators. , Halomethylthiazole compound, halomethyl-S-triazine compound, benzophenone, [4- (methylphenylthio) phenyl] phenylmethanone, ethyl anthraquinone, p-dimethylaminobenzoic acid isoamyl ester, p-dimethylaminobenzoic acid ethyl ester 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-hydroxy- Cyclohexyl-phenyl-ketone, 1- [4- (2-hydroxy Toxi) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, methylbenzoinform Mate, benzoin isobutyl ether, benzyldimethyl ketal, 2,4,6-trimethylbenzophenone, 4-methylbenzophenone, (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone, 2- [(2-Dimethylaminoethyl) amino] -4,6-bis (trichloromethyl) -S-triazine-dimethyl sulfate, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -S- Triazine, 2-methyl-4,6-bis (trichloromethyl) -S-triazine, 2,4,6-tris (tri Rolomethyl) -S-triazine, QUANTACURE ITX, ABQ, CPTX, BMS, EPD, DMB, MCA, EHA, manufactured by Octel Chemicals, TAZ-100, 101, 102, 104, 106, 107, 108, etc. manufactured by Midori Chemical Used.

  As a photopolymerization initiator contained in the photocurable material constituting the green color conversion layer 52, a photopolymerization initiator contained in the photocurable material constituting the blue color conversion layer 53, 2,4- Diethylthioxanthone, 2-chlorothioxanthone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2- [2- (furan-2-yl) ethenyl] -4,6- Bis (trichloromethyl) -S-triazine, 2- [2- (5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -S-triazine, 2- [2- (3 4-Dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -S-triazine, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxy Acylphosphine oxides such as id and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, QUANTACURE QTX manufactured by Octel Chemicals, TAZ-110, 113, 118, 120, 121, 122, manufactured by Midori Chemical 123, ESA CURE KTO46 manufactured by Lamberti or the like is used.

  As the photopolymerization initiator contained in the photocurable material constituting the red color conversion layer 51, the photopolymerization initiator contained in the photocurable material constituting the blue color conversion layer 53, bis (η5- 2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium and η5-cyclopentadienyl-η6-cumenyl-iron (1+ ) -Hexafluorophosphate (1-) metallocene, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -S-triazine, manufactured by Midori Chemical Co., Ltd. TAZ-114 or the like is used.

A light scattering layer may be applied to the color conversion layer 23 (red color conversion layer 51, green color conversion layer 52, blue color conversion layer 53).
As a material for forming the light scattering layer, it is preferable to use a material in which light scattering particles are dispersed in a resin.
As the light scattering particles, particles composed of organic materials (organic fine particles), inorganic materials or particles composed of inorganic materials (inorganic fine particles) are used, and inorganic fine particles are preferable. By using light scattering particles as a material for forming the light scattering layer, light having directivity from the outside (for example, a light emitting element) can be diffused or scattered more isotropically and effectively. In particular, by using inorganic fine particles, a light scattering layer stable to light and heat can be formed.
Moreover, it is preferable that the light scattering particles have high transparency.
In addition, the light scattering particles preferably have a higher refractive index than the resin serving as a base material.
In addition, in order for the excitation light to be effectively scattered by the light scattering layer, the particle size of the light scattering particles needs to be in the Mie scattering region, so the particle size of the light scattering particles is 100 nm to 500 nm. The degree is preferred.

  When organic fine particles are used as the light scattering particles, for example, polymethylmethacrylate beads (refractive index: 1.49), acrylic beads (refractive index: 1.50), acrylic-styrene copolymer beads (refractive index). : 1.54), melamine beads (refractive index: 1.57), high refractive index melamine beads (refractive index: 1.65), polycarbonate beads (refractive index: 1.57), styrene beads (refractive index: 1. 60), crosslinked polystyrene beads (refractive index: 1.61), polyvinyl chloride beads (refractive index: 1.60), benzoguanamine-melamine formaldehyde beads (refractive index: 1.68), silicone beads (refractive index: 1. 50) and the like.

When an inorganic material is used as the light scattering particles, for example, an oxide of at least one metal selected from the group consisting of silicon, titanium, zirconium, aluminum, indium, zinc, tin and antimony is used as a main component. Particles (fine particles).
Further, when inorganic fine particles are used as the light scattering particles, for example, silica beads (refractive index: 1.44), alumina beads (refractive index: 1.63), titanium oxide beads (refractive index anatase type: 2). .50, rutile type: 2.70), zirconia bead (refractive index: 2.05), zinc oxide bead (refractive index: 2.00), barium titanate (BaTiO ₃ ) (refractive index: 2.4) Etc.

  The resin material used by mixing with the light scattering particles and forming the light scattering layer is preferably a translucent resin. Examples of the resin material include acrylic resin (refractive index: 1.49), melamine resin (refractive index: 1.57), nylon (refractive index: 1.53), polystyrene (refractive index: 1.60), melamine. Beads (refractive index: 1.57), polycarbonate (refractive index: 1.57), polyvinyl chloride (refractive index: 1.60), polyvinylidene chloride (refractive index: 1.61), polyvinyl acetate (refractive index) : 1.46), polyethylene (refractive index: 1.53), polymethyl methacrylate (refractive index: 1.49), poly MBS (refractive index: 1.54), medium density polyethylene (refractive index: 1.53). ), High density polyethylene (refractive index: 1.54), tetrafluoroethylene (refractive index: 1.35), poly (ethylene trifluoride) chloride (refractive index: 1.42), polytetrafluoroethylene (refractive index: 1). .3 ), And the like.

Further, the surface of the color conversion layer 23 (red color conversion layer 51, green color conversion layer 52, blue color conversion layer 53) opposite to the transparent substrate 11 (hereinafter, also referred to as “one surface”). A sealing film may be provided so as to cover 23a.
The sealing film is formed by applying a resin to one surface 213a of the color conversion layer 23 using a spin coat method, ODF, or a laminate method. Alternatively, after forming an inorganic film made of SiO, SiON, SiN or the like by plasma CVD, ion plating, ion beam, sputtering, or the like so as to cover one surface 23a of the color conversion layer 23, The sealing film is formed by applying a resin using a spin coat method, ODF, a laminate method or the like so as to cover the inorganic film, or by bonding the resin film so as to cover the inorganic film. You can also.

  With this sealing film, it is possible to prevent external oxygen and moisture from being mixed into the color conversion layer 23 (the red color conversion layer 51, the green color conversion layer 52, and the blue color conversion layer 53). Deterioration of the color conversion layer 23 can be reduced. Further, when the color conversion substrate 20 is applied to a display device, oxygen and moisture contained in the color conversion layer 23 reach the liquid crystal layer, the inorganic EL element, the organic EL element, etc. Etc. can be prevented from deteriorating.

Furthermore, a planarization film may be provided so as to cover the surface of the sealing film opposite to the surface in contact with the color conversion layer 23.
The planarization film can be formed using a known material. Examples of the material for the planarizing film include inorganic materials such as silicon oxide, silicon nitride, and tantalum oxide, and organic materials such as polyimide, acrylic resin, and resist material.
Examples of the method for forming the planarization film include a dry process such as a CVD method and a vacuum deposition method, and a wet process such as a spin coating method. However, the present embodiment is limited to these materials and the formation method. is not.
Further, the planarization film may have either a single layer structure or a multilayer structure.
By this flattening film, when the color conversion substrate 20 is combined with an organic light source or a liquid crystal layer, it is possible to prevent a gap from being generated between the color conversion substrate 20 and the organic light source or the liquid crystal layer, and color conversion. The adhesion between the substrate 20 and the organic light source or the liquid crystal layer can be improved.

On one surface 21a of the transparent substrate 21, each pixel (red pixel 31, green pixel 32, blue pixel 33) composed of the color conversion layer 23 (red color conversion layer 51, green color conversion layer 52, blue color conversion layer 53). A light-absorbing partition wall 24 is provided between them. The partition wall 24 absorbs light emitted by the phosphor of the color conversion layer 23 (red color conversion layer 51, green color conversion layer 52, blue color conversion layer 53), and between adjacent pixels of the color conversion substrate 20, The contrast of the luminescent color can be improved.
The film thickness of the partition wall 24 is usually about 100 nm to 100 μm, but preferably 100 nm to 10 μm.

Moreover, it is preferable that the partition wall 24 forms a light reflective or light scattering bank. As a result, out of isotropic light emission from the color conversion layer 23 (red color conversion layer 51, green color conversion layer 52, blue color conversion layer 53), light is emitted in the lateral direction (waveguide component through the color conversion layer 23). Thus, the light emission loss component that cannot be extracted to the transparent substrate 21 side is reflected and scattered in a desired pixel by a light reflective or light scattering bank so that the light emission can be used effectively. Accordingly, it is possible to prevent a decrease in color purity due to leakage of light emission to other than the desired pixel. In addition, the light emitted from the color conversion layer 23 can be reflected in each pixel, and the light emission from the color conversion layer 23 can be used effectively, so that the light emission efficiency can be improved and the power consumption can be reduced. Can be reduced.
Further, the film thickness of the light reflective or light scattering bank is preferably larger than the total film thickness of the color conversion layer 23. As a result, it is possible to effectively use a light emission loss component that is guided in the color conversion layer 23 and emits light in the side surface direction and cannot be extracted to the transparent substrate 21 side.

  The material for forming the light-reflective or light-scattering bank is not particularly limited, and examples thereof include a reflective film such as a metal such as gold, silver, and aluminum, and a scattering film such as titanium oxide.

Examples of the material of the partition wall 24 include inorganic materials such as silicon oxide (SiO ₂ ), silicon nitride (SiN or Si ₂ N ₄ ), tantalum oxide (TaO or Ta ₂ O ₅ ), or acrylic resin. And organic materials such as resist materials, metals such as gold, silver, and aluminum.
By using a metal as the material of the partition wall 24, it is possible to reflect the light emitted from the phosphor contained in the color conversion layer 23 and to emit light only in a desired direction, thereby improving the light emission efficiency. This is preferable because it is possible. In addition, when the partition wall 24 itself is not reflective, it is possible to reflect light emitted from the phosphor contained in the color conversion layer 23 in a desired direction by forming a metal reflective film on the partition wall 24. Examples of the method for forming a reflective film made of metal on the partition wall 24 include a dry process such as a chemical vapor deposition (CVD) method and a vacuum deposition method, and a wet process such as a spin coating method. Moreover, as a patterning method of the partition wall 24, a conventional photolithography method or the like can be given.

  In the color conversion substrate 20 of this embodiment, the emission peak wavelength of external light is preferably 380 nm or more and 470 nm or less.

Next, an example of a method for manufacturing a color conversion substrate will be described.
(Formation of black matrix)
A 5-inch glass substrate having a thickness of 0.7 mm was washed with water, followed by pure water ultrasonic cleaning for 10 minutes, acetone ultrasonic cleaning for 10 minutes, and 2-propanol vapor cleaning for 5 minutes in this order. The glass substrate is dried for 1 hour.
Next, a BK resist (manufactured by Tokyo Ohka Kogyo Co., Ltd.) is applied as a black matrix forming composition onto a glass substrate that has been cleaned by spin coating, and prebaked at 70 ° C. for 15 minutes to form a coating film having a thickness of 1 μm. . On this coating film, a photomask (pixel pitch 57 μm, line width 6 μm, subpixel size 13 μm × 51 μm) for forming a target pattern is set, and i-line is irradiated at an exposure amount of 100 mJ / cm ² . Expose the coating. Subsequently, it develops using sodium carbonate aqueous solution as a developing solution, and performs the rinse process with a pure water, and forms the black matrix of a pixel pattern shape with a film thickness of 1 micrometer.

(Formation of partition walls)
Next, on the glass substrate on which a black matrix is formed using a positive resist composed of an acrylic resin, a naphthoquinone diazide sulfonate ester, a coupling agent, a photoacid generator, and an organic solvent as a partition wall forming composition. The bank forming composition is applied by spin coating, and prebaked at 90 ° C. for 2 minutes to form a coating film having a thickness of 10 μm. On this coating film, a photomask designed so that a partition is formed on a black matrix is installed, and i-line is irradiated at an exposure amount of 300 mJ / cm ² to expose the coating film.
Next, development is performed using a tetramethylammonium aqueous solution to obtain a pixel-patterned structure. Subsequently, after post-exposure (irradiation of i-line with an exposure amount of 300 mJ / cm ² ), post-baking is performed at 220 ° C. for 1 hour, thereby forming a partition wall having a thickness of 8 μm.

(Formation of reflective layer)
Next, after 100 nm of aluminum is formed on the surface of the substrate on which the barrier ribs are formed by vacuum deposition, an existing positive resist for forming a metal thin film pattern is applied by spin coating to cover the entire surface of the substrate including the barrier ribs.
Next, exposure is performed through a photomask designed to leave the positive resist in the partition region, and development and immersion in an aluminum etching solution remove the aluminum thin film in the pixel region.
Next, the positive resist remaining in the partition region is removed by immersing in acetone, and a reflective layer made of aluminum is formed only on the surface of the partition.

(Formation of color conversion layer)
Next, a red color filter, a green color filter, and a blue color filter are formed by patterning using an existing photolithography method in each subpixel region partitioned by the partition wall on which the reflective layer is formed. The film thicknesses of these color filters are all 2 μm.
Next, as the red conversion material, the binuclear complex of the first embodiment described above (blue to red color conversion material) is added in an amount of 1% by mass with respect to the resin component in the existing negative resist, A solution (a composition for a red color conversion layer) is obtained by applying a sound wave to dissolve.
Next, the obtained solution is applied to a substrate on which a reflective layer, partition walls, and a black matrix are formed, and a coating film is obtained by a spin coating method.
Next, the i-line of the parallel light is applied to the obtained coating film through a photomask designed to irradiate only the sub-pixel region where the red color filter is formed, which is partitioned by the partition wall. Irradiate at 600 mJ / cm ² to cure the coating. Furthermore, the glass substrate provided with this hardened | cured material is immersed in 2-propanol, and it develops by dissolving the coating film of an unexposed part, and forms a pattern. And the red color conversion layer is formed by heating the glass substrate in which this pattern was formed on a 90 degreeC hotplate, and removing the remaining solvent.
Next, a green conversion layer containing the material is formed in the same manner as the red conversion material except that the binuclear complex (blue to green color conversion material) of the first embodiment is used as the green conversion material. It is formed only in the sub-pixel region where the green color filter is formed. The film thicknesses of the red conversion layer and the green conversion layer at this time are both 5 μm.

(Formation of light scattering layer)
Next, titanium oxide having an average particle diameter of 200 nm as light scattering particles is added to an epoxy resin (“SU-8” manufactured by Nippon Kayaku Co., Ltd.), which is a binder resin, and thoroughly mixed in an automatic mortar. The composition for light-scattering layer formation is prepared by stirring this for 15 minutes using "Filmix (trademark) 40-40 type | mold" by a company.
Next, the obtained composition for forming a light scattering layer is applied onto a glass substrate formed up to the green conversion layer, and a coating film is formed by a spin coating method.
The resulting coating film is then subjected to parallel light i-line through a photomask designed to irradiate light only to the sub-pixel region where the blue color filter is formed in a nitrogen atmosphere. Irradiate at 600 mJ / cm ² to cure the coating. Furthermore, the glass substrate provided with this hardened | cured material is immersed in the organic solvent, and it develops by dissolving the coating film of an unexposed part, and forms a pattern. And the light-scattering layer (blue light-scattering layer) is formed by heating the glass substrate in which this pattern was formed on a 90 degreeC hotplate, and removing the remaining solvent. The thickness of the obtained light scattering layer is 4 μm.

The color conversion board | substrate which used the above-mentioned 1st Embodiment binuclear complex as a color conversion material by the above is obtained.
The obtained color conversion substrate is provided with a blue light emitting organic electroluminescence element as a blue incident light source, or a blue backlight with light transmission and light shielding switching by liquid crystal or microelectromechanical system (MEMS). By using the substrate, a color conversion display capable of color display can be obtained.

[Fourth Embodiment] (Lighting Device)
The illumination device of the present embodiment includes the light emitting element of the second embodiment described above.

Hereinafter, the illumination device of the present embodiment will be described in detail with reference to FIGS. 5 and 6.
FIG. 5 is a schematic perspective view showing a ceiling light as a first example of the lighting apparatus according to the present embodiment.
The ceiling light 60 of the present embodiment is generally configured by a light emitting unit 61, a hanging line 62, and a power cord 63. And the light emission part 61 is comprised from the light emitting element of the above-mentioned 2nd Embodiment.

FIG. 6 is a schematic perspective view showing a lighting stand as a second example of the lighting device of the present embodiment.
The illumination stand 70 of the present embodiment is generally configured by a light emitting unit 71, a stand 72, a main switch 73, and a power cord 74. And the light emission part 71 is comprised from the light emitting element of the above-mentioned 2nd Embodiment.

The ceiling light 60 of the present embodiment is particularly excellent in luminous efficiency because the light emitting unit 61 is composed of the light emitting element of the second embodiment described above.
In addition, the illumination stand 70 of the present embodiment is particularly excellent in luminous efficiency because the light emitting unit 71 is composed of the light emitting element of the second embodiment described above.
The lighting device of the above-described embodiment is suitable for application to various electronic devices.

[Fifth Embodiment] (Electronic Device)
The electronic device of the present embodiment includes the light emitting element of the second embodiment described above.

Hereinafter, the electronic apparatus of this embodiment will be described in detail with reference to FIGS.
FIG. 7 is a schematic front view showing a mobile phone as a first example of the electronic apparatus of the present embodiment.
The cellular phone 80 according to the present embodiment is generally configured by an audio input unit 81, an audio output unit 82, an antenna 83, an operation switch 84, a display unit 85, and a housing 86. The display unit 85 includes the light emitting element of the second embodiment described above as a backlight.

FIG. 8 is a schematic front view showing a thin television as a second example of the electronic apparatus of the present embodiment.
The thin television 90 according to the present embodiment is generally configured by a display unit 91, a speaker 92, a cabinet 93, and a stand 94. And the display part 91 is provided with the light emitting element of the above-mentioned 2nd Embodiment as a backlight.

FIG. 9 is a schematic front view showing a portable game machine as a third example of the electronic apparatus of the present embodiment.
A portable game machine 100 according to the present embodiment is roughly configured from operation buttons 101 and 102, an external connection terminal 103, a display unit 104, and a housing 105. The display unit 104 includes the light emitting element of the second embodiment described above as a backlight.

FIG. 10 is a schematic perspective view showing a notebook computer as a fourth example of the electronic apparatus of the present embodiment.
The notebook personal computer 110 according to the present embodiment is schematically configured by a display unit 111, a keyboard 112, a touch pad 113, a main switch 114, a camera 115, a recording medium slot 116, and a housing 117. And the display part 111 is equipped with the light emitting element of the above-mentioned 2nd Embodiment as a backlight.

  Since any of the electronic devices of the above-described embodiment includes the light-emitting element of the above-described second embodiment, an image can be displayed with particularly excellent light emission efficiency.

  As mentioned above, although preferred embodiment which concerns on this invention was described, it cannot be overemphasized that this invention is not limited to these. Various shapes, combinations, and the like of the constituent members shown in the above-described embodiments are merely examples, and various modifications can be made based on design requirements and the like without departing from the gist of the present invention.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to a following example.

[Example 1]
As a synthetic raw material, Europium acetate monohydrate (Europium acetate n hydrate / Eu (CH ₃ COO) ₃ nH ₂ O; purity 99.9%, manufactured by Rare Metallic), 2,4-Pentanedione, 1,1, 1,5,5,5-hexafluoro (hexafluoroisopropanol penta-dione _{/ C 5 H 2 F 6 O} 2; CAS.1522-22-1, 95% purity, manufactured by Tokyo Chemical Industry Co., Ltd.) was used.
Assuming that n = 2, the molecular weight of europium acetate is about 365.13 [g / mol]. The molecular weight of hexafluoropentadione is about 208.06 [g / mol].
7.020 g of europium acetate powder was weighed and put into a three-necked flask.
Next, 50 mL of pure water was charged into the three-necked flask. Using a rotor, the europium acetate powder was dissolved in pure water while stirring at room temperature.
Next, about 10 g of hexafluoropentadione was weighed and slowly dropped into a europium acetate aqueous solution using a dropping funnel. The molar ratio of europium acetate and hexafluoropentadione is about 1: 2.5.
After completion of the dropping, the mixed solution was stirred using a rotor for about 3 hours at room temperature and in the atmosphere. The mixed solution gradually became cloudy and a solid was precipitated. After stirring for 3 hours, suction filtration was performed to separate the precipitate.
By this step, about 11.18 g of a solid product (europium binuclear complex) was obtained.

Next, in order to improve the crystallinity of the obtained solid composite, a recrystallization step with a methanol-water mixed solvent was performed twice.
First, using a beaker, a solid compound (europium binuclear complex) was added to about 50 mL of methanol, which is a good solvent, and completely dissolved at room temperature.
Subsequently, the pure water which is a poor solvent was added little by little to the europium binuclear complex solution at room temperature, and the pure water was continuously added until the solution became cloudy.
When the solution became cloudy, the temperature of the solution was raised to about 65 ° C. to completely dissolve the precipitate. The amount of pure water added at this time was about 38 mL.
This solution was left in a box with high thermal insulation for about 1 day to cool the solution slowly. As a result, white rod-like crystals were precipitated.
The crystals were then separated from the solution by suction filtration.
The above process (recrystallization process) was performed twice. As a result, the finally obtained crystal (europium binuclear complex) was 4.41 g.

(Single crystal X-ray structure analysis)
In order to identify the structure of the obtained crystal, single crystal X-ray structural analysis was performed.
As a single crystal X-ray structural analysis apparatus, “XtaLAB P200 MM007HF-DW” (manufactured by Rigaku Corporation) was used.
The sample size was 0.13 mm × 0.02 mm × 0.001 mm.
The crystals were snap frozen with a gas stream in a cryostat.
The measurement temperature was −180 ° C.
The X-ray source was CuKα (λ = 1.54187Å).
As a result of analyzing the diffraction data, it was confirmed that the europium binuclear complex (binuclear complex represented by the general formula (6)) shown in FIG. 2 was obtained.

(Fourier transform infrared spectroscopy)
A Fourier transform infrared spectroscopic (FT-IR) spectrum was measured on the obtained crystal by the KBr method.
Wave number [nu = 1650 cm ^-1 corresponding to stretching vibration of C = O, and, since the absorption peak near the wave number ν ⁼ 1145cm ^-1 ~1258cm -1 corresponding to stretching vibration of C-F is obtained, the formula It was estimated that the anion ((C ₅ O ₂ HF ₆ ) ⁻ ) of hexafluoroacetylacetone (C ₅ O ₂ H ₂ F ₆ ) represented by (10) was coordinated.

(Liquid chromatography measurement)
Liquid chromatography measurement was performed on the obtained crystals.
Acetonitrile was used as the solvent, and a reverse phase column was used as the column (reverse phase chromatography).
The time change of the absorbance of ultraviolet light having a wavelength of 254 nm was monitored.
As a result, since the absorbance peak was a single peak, it was assumed that the synthesized europium binuclear complex had a substance with almost a single composition.

Moreover, the excitation spectrum and emission spectrum of the obtained europium binuclear complex (C ₂₄ H ₁₈ Eu ₂ F ₂₄ O ₁₆ ) were measured using an excitation / emission spectrum measurement apparatus Fluoro Max-4 (manufactured by Horiba Seisakusho). . In the measurement of the excitation spectrum, the light detection wavelength was 614 nm. In the measurement of the emission spectrum, the excitation wavelength was 450 nm. The measurement result of the excitation spectrum is shown in FIG. The measurement results of the emission spectrum are shown in FIG.
From the result of FIG. 11, the excitation band of the europium binuclear complex (C ₂₄ H ₁₈ Eu ₂ F ₂₄ O ₁₆ ) was a wavelength of 250 nm to 475 nm, which was spread over a wide band, and the excitation spectrum was broad. From the results shown in FIG. 12, the europium binuclear complex (C ₂₄ H ₁₈ Eu ₂ F ₂₄ O ₁₆ ) had an emission peak wavelength of 614 nm and a sharp emission spectrum.

[Example 2]
As a synthetic raw material, terbium acetate monohydrate (terbium acetate n hydrate / Eu (CH ₃ COO) ₃ nH ₂ O; purity 99.9%, manufactured by Rare Metallic), 2,4-Pentanedione, 1,1, 1,5,5,5-hexafluoro (hexafluoroisopropanol penta-dione _{/ C 5 H 2 F 6 O} 2; CAS.1522-22-1, 95% purity, manufactured by Tokyo Chemical Industry Co., Ltd.) was used.
Assuming n = 2, the molecular weight of terbium acetate is about 372.09 [g / mol]. The molecular weight of hexafluoropentadione is about 208.06 [g / mol].
7.153 g of terbium acetate powder was weighed and put into a three-necked flask.
Next, 50 mL of pure water was charged into the three-necked flask. The terbium acetate powder was dissolved in pure water while stirring at room temperature using a rotor.
Next, about 10 g of hexafluoropentadione was weighed and slowly dropped into an aqueous terbium acetate solution using a dropping funnel. The molar ratio of terbium acetate and hexafluoropentadione is about 1: 2.5.
After completion of the dropping, the mixed solution was stirred using a rotor for about 3 hours at room temperature and in the atmosphere. The mixed solution gradually became cloudy and a solid was precipitated. After stirring for 3 hours, suction filtration was performed to separate the precipitate.
By this step, about 10.206 g of a solid compound (terbium binuclear complex) was obtained.

Next, in order to improve the crystallinity of the obtained solid composite, a recrystallization step with a methanol-water mixed solvent was performed twice.
First, using a beaker, a solid compound (terbium binuclear complex) was added to about 50 mL of methanol, which is a good solvent, and completely dissolved at room temperature.
Subsequently, the pure water which is a poor solvent was added little by little to the terbium dinuclear complex solution at room temperature, and the pure water was continuously added until the solution became cloudy.
When the solution became cloudy, the temperature of the solution was raised to about 65 ° C. to completely dissolve the precipitate. The amount of pure water added at this time was about 38 mL.
This solution was left in a box with high thermal insulation for about 1 day to cool the solution slowly. As a result, white rod-like crystals were precipitated.
The crystals were then separated from the solution by suction filtration.
The above process (recrystallization process) was performed twice. As a result, the finally obtained crystal (terbium binuclear complex) was 3.975 g.

The excitation spectrum and emission spectrum of the obtained terbium binuclear complex (C ₂₄ H ₁₈ Tb ₂ F ₂₄ O ₁₆ ) were measured using an excitation / emission spectrum measuring apparatus Fluoro Max-4 (manufactured by Horiba Seisakusho). In the measurement of the excitation spectrum, the light detection wavelength was set to 542 nm. In the measurement of the emission spectrum, the excitation wavelength was 450 nm. The measurement results of the excitation spectrum are shown in FIG. The measurement results of the emission spectrum are shown in FIG.
From the results shown in FIG. 13, the excitation band of the terbium binuclear complex (C ₂₄ H ₁₈ Tb ₂ F ₂₄ O ₁₆ ) was a wavelength of 300 nm to 450 nm and was spread over a wide band, and the excitation spectrum was broad. From the results shown in FIG. 14, the terbium binuclear complex (C ₂₄ H ₁₈ Tb ₂ F ₂₄ O ₁₆ ) had an emission peak wavelength of 540 nm and a sharp emission spectrum.

[Example 3]
As synthetic raw materials, Samarium acetate monohydrate (Samarium acetate n hydrate / Sm (CH ₃ COO) ₃ nH ₂ O; purity 99.9%, manufactured by Rare Metallic), 2,4-Pentanedione, 1,1, 1,5,5,5-hexafluoro (hexafluoroisopropanol penta-dione _{/ C 5 H 2 F 6 O} 2; CAS.1522-22-1, 95% purity, manufactured by Tokyo Chemical Industry Co., Ltd.) was used.
Assuming that n = 2, the molecular weight of samarium acetate is about 363.52 [g / mol]. The molecular weight of hexafluoropentadione is about 208.06 [g / mol].
6.987 g of samarium acetate powder was weighed and put into a three-necked flask.
Next, 50 mL of pure water was charged into the three-necked flask. Using a rotor, samarium acetate powder was dissolved in pure water while stirring at room temperature.
Next, about 10 g of hexafluoropentadione was weighed and slowly added dropwise to the aqueous samarium acetate solution using a dropping funnel. The blending molar ratio of samarium acetate and hexafluoropentadione is about 1: 2.5.
After completion of the dropping, the mixed solution was stirred using a rotor for about 3 hours at room temperature and in the atmosphere. The mixed solution gradually became cloudy and a solid was precipitated. After stirring for 3 hours, suction filtration was performed to separate the precipitate.
By this step, about 10.307 g of a solid compound (samarium binuclear complex) was obtained.

Next, in order to improve the crystallinity of the obtained solid composite, a recrystallization step with a methanol-water mixed solvent was performed twice.
First, using a beaker, a solid compound (samarium binuclear complex) was added to about 50 mL of methanol, which is a good solvent, and completely dissolved at room temperature.
Next, pure water as a poor solvent was added to the samarium dinuclear complex solution little by little at room temperature, and pure water was continuously added until the solution became cloudy.
When the solution became cloudy, the temperature of the solution was raised to about 65 ° C. to completely dissolve the precipitate. The amount of pure water added at this time was about 38 mL.
This solution was left in a box with high thermal insulation for about 1 day to cool the solution slowly. As a result, white rod-like crystals were precipitated.
The crystals were then separated from the solution by suction filtration.
The above process (recrystallization process) was performed twice. As a result, the finally obtained crystal (samarium binuclear complex) was 4.068 g.

The excitation spectrum and emission spectrum of the obtained samarium binuclear complex (C ₂₄ H ₁₈ Sm ₂ F ₂₄ O ₁₆ ) were measured using an excitation / emission spectrum measurement apparatus Fluoro Max-4 (manufactured by Horiba Seisakusho). In the measurement of the excitation spectrum, the light detection wavelength was 641 nm. In the measurement of the emission spectrum, the excitation wavelength was 400 nm. The measurement result of the excitation spectrum is shown in FIG. The measurement results of the emission spectrum are shown in FIG.
From the results shown in FIG. 15, the excitation band of the samarium binuclear complex (C ₂₄ H ₁₈ Sm ₂ F ₂₄ O ₁₆ ) is a wavelength of 300 nm to 460 nm, spread over a wide band, and the excitation spectrum is broad. From the results of FIG. 16, the samarium binuclear complex (C ₂₄ H ₁₈ Sm ₂ F ₂₄ O ₁₆ ) has an emission peak wavelength of 640 nm and a sharp emission spectrum.

  As described above, the rare earth complexes of Examples 1 to 3 also have an excitation band at 400 nm to 450 nm, which is an excitation wavelength when using a near ultraviolet LED element or a blue LED element widely used as an excitation light source for white LEDs. Since the emission peak wavelength is in the range of 540 nm to 640 nm, it can be applied to a white LED in combination with a generally used near ultraviolet LED element or blue LED element.

  The present invention can be used for white LEDs.

DESCRIPTION OF SYMBOLS 10 ... White light emitting diode (white LED), 11 ... Semiconductor light emitting element, 13 ... Phosphor (green phosphor), 14 ... Phosphor (red phosphor), 15 ... Frame , 16 (16A, 16B) ... lead frame, 17 ... bonding wire, 18 ... sedimentation inhibitor.

Claims (19)

A binuclear complex having a basic skeleton in which a first complex structure and a second complex structure are paired;
The first complex structure and the second complex structure are formed by chemically bonding a rare earth element cation to a carboxylate anion,
One oxygen of the first complex structure is bonded to the rare earth element cation in the first complex structure,
2. The binuclear complex, wherein the other oxygen of the first complex structure is bonded to the rare earth cation in the first complex structure and the rare earth cation in the second complex structure. The binuclear complex according to claim 1, wherein the basic skeleton is represented by the following general formula (1).

(In the formula, R represents a hydrogen atom, a deuterium atom, a hydrocarbon group represented by C _n H _m , or a group obtained by substituting H with another element from a hydrocarbon represented by C _n H _m X. A represents at least one cation selected from the group consisting of Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu, and X represents a halogen atom. Represents an oxygen atom, a nitrogen atom, a sulfur atom, or a phosphorus atom.)   Each of the rare earth element cation of the first complex structure and the rare earth element cation of the second complex structure has a photosensitizing ligand that absorbs light and supplies the light energy to the rare earth element cation. The binuclear complex according to claim 1 or 2, wherein one coordinate bond is formed.   Each of the rare earth element cation of the first complex structure and the rare earth element cation of the second complex structure has 2 photosensitizing ligands that absorb light and supply the light energy to the rare earth element cation. The binuclear complex according to claim 3, wherein the binuclear complex is a single or three coordinate bond.   The binuclear complex according to claim 3 or 4, wherein the ligand has at least π conjugation.   The binuclear complex according to any one of claims 3 to 5, wherein the ligand is a bidentate ligand. The binuclear complex according to any one of claims 1 to 6, wherein the ligand is represented by the following general formulas (2) to (4).

(In the formula, ^{R 1} and ^{R 2} are each _{independently} a C n _H hydrocarbon group represented by _m, C n _{H m} have been substituted by hydrocarbon H to another element represented by X D represents a hydrogen atom, a deuterium atom, a halogen atom, a hydrocarbon group represented by C _n H _m , or a group in which H is substituted with another element from a hydrocarbon represented by C _n H _m X X represents a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a selenium atom, or a phosphorus atom.)

(Wherein, ^{R 3} and ^{R 4} are each _{independently} a C n _H hydrocarbon group represented by _m, C n _{H m} have been substituted by hydrocarbon H to another element represented by X X represents a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a selenium atom, or a phosphorus atom.)

(Wherein, ^{R 5} and ^{R 6} are each _{independently} a C n _H hydrocarbon group represented by _m, C n _{H m} have been substituted by hydrocarbon H to another element represented by X X ¹ and X ² each independently represent a group IVb atom excluding carbon, a group Vb atom excluding nitrogen, and a group VIb atom excluding oxygen, and Y represents a halogen atom, oxygen atom, nitrogen atom, sulfur An atom, a selenium atom, or a phosphorus atom, and a and b each independently represent 0 or 1.) The binuclear complex according to any one of claims 1 to 5, wherein the ligand is represented by the following general formula (5).

(In the formula, R ⁷ represents a hydrocarbon represented by C _n H _m , or a group obtained by substituting H with another element from a hydrocarbon represented by C _n H _m X. X ³ represents carbon. And represents a group IVb atom excluding nitrogen, a group Vb atom excluding nitrogen, and a group VIb atom excluding oxygen, and c represents 0 or 1.) A semiconductor light emitting element, a resin surrounding the entire semiconductor light emitting element, and at least two phosphors dispersed in the resin and excited by light emitted from the semiconductor light emitting element to emit fluorescence having a wavelength different from the excitation wavelength And comprising
One of said two fluorescent substance consists of a binuclear complex of any one of Claims 1-8, The light emitting element characterized by the above-mentioned.   The light emitting element according to claim 9, wherein an emission peak wavelength of light emitted from the semiconductor light emitting element is 380 nm or more and 470 nm or less. The binuclear complex contains at least Eu,
The emission peak wavelength of the binuclear complex is 605 nm or more and 620 nm or less,
11. The light-emitting element according to claim 9, wherein the full width at half maximum of the emission peak of the binuclear complex is 15 nm or less. The binuclear complex includes at least Tb;
The emission peak wavelength of the binuclear complex is 535 nm or more and 550 nm or less,
11. The light-emitting element according to claim 9, wherein the full width at half maximum of the emission peak of the binuclear complex is 15 nm or less. The binuclear complex includes at least Sm;
The emission peak wavelength of the binuclear complex is 635 nm or more and 650 nm or less,
11. The light-emitting element according to claim 9, wherein the full width at half maximum of the emission peak of the binuclear complex is 15 nm or less. A transparent substrate having light transparency, and a color conversion layer that is provided on one surface of the transparent substrate and is excited by external light to emit light having a wavelength different from the excitation wavelength,
The said color conversion layer contains the binuclear complex of any one of Claims 1-8, The color conversion board | substrate characterized by the above-mentioned.   The color conversion substrate according to claim 14, wherein an emission peak wavelength of the external light is 380 nm or more and 470 nm or less. The binuclear complex contains at least Eu,
The emission peak wavelength of the binuclear complex is 605 nm or more and 620 nm or less,
The color conversion substrate according to claim 14 or 15, wherein the full width at half maximum of the emission peak of the binuclear complex is 15 nm or less. The binuclear complex includes at least Tb;
The emission peak wavelength of the binuclear complex is 535 nm or more and 550 nm or less,
The color conversion substrate according to claim 14 or 15, wherein the full width at half maximum of the emission peak of the binuclear complex is 15 nm or less. The binuclear complex includes at least Sm;
The emission peak wavelength of the binuclear complex is 635 nm or more and 650 nm or less,
The color conversion substrate according to claim 14 or 15, wherein the full width at half maximum of the emission peak of the binuclear complex is 15 nm or less.   An electronic apparatus comprising at least one of the light emitting element according to any one of claims 9 to 13 and the color conversion substrate according to any one of claims 14 to 18.

Images