KR100897260B1 - White emitting nanoparticles?dispersion and organic photoelectric device thereby - Google Patents

Abstract

Since the energy transfer efficiency from the host to the dopant is excellent, when applied to the light emitting layer of the organic photoelectric device, a white light emitting nanoparticle dispersion liquid for an organic photoelectric device which can increase the overall luminous efficiency is provided. The white light-emitting nanoparticles for an organic photoelectric device according to the present invention are red (R) -green (G) -blue (in which a dopant compound selected from a host compound, a dye, a dye, and a metal complex is dispersed in a dispersion medium containing a dispersant). B) a mixture of each of the light emitting nanoparticle dispersion, or a mixture of each of the yellow (Y) -blue (B) light emitting nanoparticle dispersion in which the host compound and the dopant compound are dispersed in the dispersant and the dispersion medium. .

White nanoparticles, organic photoelectric device, light emitting layer, dispersant

Description

White emitting nanoparticle dispersion and organic photoelectric device using the same

1 is an electron micrograph of the nanoparticles prepared in Example 4.

2 is an electron micrograph of the nanoparticles prepared in Example 5.

3 is an electron micrograph of the nanoparticles prepared in Example 7.

Figure 4 is an electron micrograph of the nanoparticles prepared in Example 8.

5 is a graph showing light emission spectra of Examples 4, 5, 7, and 8;

6 is a graph showing light emission spectrum measurement results for Example 8 and Comparative Example 1. FIG.

7 is a light intensity measurement results for the nanoparticle film prepared in Examples 1′-5

8 is a light intensity measurement results for the nanoparticle film prepared in Examples 6′-8

The present invention relates to a white light emitting nanoparticle dispersion and an organic photoelectric device using the same, and more particularly, a dopant in a white light emitting nanoparticle for forming an emission layer of an organic photoelectric device including a host and a dopant. By using dyes, dyes or metal complexes as artificial, and artificially controlling the distance between the host and the dopant, the efficiency of energy transfer from the host to the dopant can be increased, and ultimately, when applied to the organic photoelectric device, the luminous efficiency can be increased. The present invention relates to a white light emitting nanoparticle dispersion for an organic photoelectric device and an organic photoelectric device using the same.

An optoelectronic device is a device that converts light energy into electrical energy or vice versa in a broad sense. Examples of such an optoelectronic device include an organic electroluminescent device, a solar cell, and a transistor.

Among such optoelectronic devices, organic light emitting diodes (OLEDs), in particular, have attracted great attention as flat-panel display (FPD) technology is recently developed.

Organic electroluminescent device (OLED) is an active light emitting display device that uses light phenomena when electrons and holes combine in the thin film when current flows through the light emitting compound thin film. High efficiency, high image quality, low driving voltage, and low power consumption. In addition to the advantages of fast response speed and wide viewing angle, the manufacturing process is simple and economical, and many researches are being conducted on the next-generation flat panel display fields such as portable electronic devices.

In particular, white light emitting devices are drawing attention as a next-generation light source due to an increase in demand for human-friendly emotional lighting due to reduction of energy resources and quality of life. Applications of white light emitting devices include display light source fields used as backlight units for IT devices such as mobile phones, fluorescent light bulbs, incandescent lamps, interior light replacements, LED billboards, traffic signals, automotive lamps, landscape lighting, indoor and outdoor lighting light sources, etc. And active research is underway.

Organic electroluminescence has been realized using anthracene single crystals by M. Pope ( J. Chem . Phys ., 42 , 2540,1965) and W. Helfrich ( Phys . Rev. Lett . 14 , 229, 1965). Although steady commercialization has been conducted, commercialization has not been achieved due to a decrease in luminous efficiency and shortening of device lifetime.In 1987, CWTang ( Apply ., Phys ., Lett . , 51 , 913 (1987).) Active research has been conducted since the development of a green light emitting device having a low driving voltage and improved efficiency and stability by forming a double layer low molecular organic material thin film composed of a light emitting layer.

In the case of using only one material as a light emitting material, excimer is formed by the interaction between molecules and the luminous efficiency is reduced, or the maximum emission wavelength is moved to the long wavelength by the intermolecular interaction, so the color purity is lowered and the photoelectricity is reduced. There is a drawback to shortening the lifetime of the device (Photophysics of Aromatic Molecules. London, UK., Wiley-nterscience, 1970, p. 569).

Therefore, in order to improve color purity and increase luminous efficiency due to energy transfer, dopant-host emission systems are frequently used. In general, energy transfer from the host material to the dopant is achieved by post energy transfer by dipole-dipole interactions and dex energy transfer by transfer of intermolecular electrons. It increases as distance is close. In general, the concentration of the dopant is increased to shorten the distance between the host and the dopant. In this case, when the doping concentration is increased, energy transfer occurs well, but at a high concentration, there is a problem in that concentration quenching decreases in luminous efficiency. . ( Applied physics letters , 74 , 442, 1999)

J. Kido ( Appl ., Phys ., Lett ., 64 , 815, (1994).) Developed a white light emitting device using red, green and blue dopants simultaneously and using PVK as a host. In this case, since the exciton energy levels of the dopants are different, it is difficult to precisely adjust the molar ratio of each dopant for emitting white light. In addition, since the dopant used as a light emitter exists in a molecular state in the PVK matrix of the polymer, which is a host material, durability, such as a change in color coordinates due to a decrease in thermal stability and a lifetime characteristic of the device, is reduced.

In order to suppress concentration quenching between dopant materials, to prevent degradation of light emitting materials, and to improve device stability, studies on using a dendrima compound with a metal complex have been conducted. However, the efficiency of recombination of holes and electrons is reduced, The energy transfer efficiency from the excitation triplet of the host compound produced by recombination to the metal complex is low, resulting in low luminous efficiency and high driving voltage. ( Applied physics letters , 80 , 2645, 2002)

Japanese Patent Laid-Open No. 2006-96697 discloses an organometallic complex in a clathrate compound by using a bonding force such as ionic bond force, ion-dipole interaction, hydrogen bond, charge transfer interaction, coordination bond, van der Waals bond, and pi-pie interaction. A description is given of the particulate dispersion of the phosphorescent organometallic complex prepared by bonding. Types of clathrate compounds used in the complex include crown ether derivatives, cyclophane derivatives, calixarene compounds, carbon nanotube derivatives, cyclodextrin derivatives, and criptand derivatives. And so on. However, the clathrate compound requires a functional group capable of transporting electrons or electrons in order to have a function of an optoelectronic device, and has a disadvantage in that it takes more than 12 hours to synthesize a clathrate compound having such a functional group. There is a disadvantage in that the synthesis yield of the clathrate compound is lowered during the various preparation steps. Once the clathrate compound is prepared, it reacts with the metal complex again to synthesize the complex, and thus the entire manufacturing process is very complicated. In particular, since the metal complex exists by chemical bonding to the clathrate compound, in this case, the energy between the HOMO and LUMO of the metal complex There is a problem that the gap is affected and the color purity is lowered. In addition, when nanoparticles containing metals, such as metal complexes, are manufactured in nanoscale, there is a disadvantage in that a uniform film cannot be practically produced during device fabrication due to secondary particle generation and precipitation in microparticle coagulation.

M. Granstrom ( Appl ., Phys ., Lett ., 68 , 147, (1996).) Has produced a white light emitting device using a polymer compound. In this case, the process is simple and a large-area device can be manufactured. However, as compared with the white light emitting device using the low molecular weight dopant, the driving voltage is high, and thus, the lifetime is low and the luminous efficiency is low.

The technical problem to be achieved by the present invention is excellent dispersion stability, has a high luminous efficiency by removing defects on the surface of the nanoparticles, when applied to the light emitting layer of the organic photoelectric device, it is possible to produce a uniform thin film, the overall luminous efficiency To provide a white light emitting nanoparticle dispersion for organic photoelectric device that can increase the.

Another object of the present invention is to provide a white light emitting device manufactured by using the compound for an organic photoelectric device as a light emitting layer.

The white light emitting nanoparticle dispersion liquid for an organic photoelectric device according to the first embodiment of the present invention for solving the above technical problem is dispersed in a dispersion medium containing a dispersant a dopant compound selected from a host compound, a dye, a dye and a metal complex. Each of the red (R) -green (G) -blue (B) luminescent nanoparticle dispersions or each of the yellow (Y) -blue (B) in which the host compound and the dopant compound are dispersed in the dispersant and the dispersion medium. It is characterized by being prepared by mixing the light emitting nanoparticle dispersion.

The white light-emitting nanoparticle dispersion liquid for an organic photoelectric device according to the second embodiment of the present invention for solving the above technical problem is a red light emitting dopant, a green light emitting dopant, a blue selected from a host compound, a dye, a dye and a metal complex And a light emitting dopant is mixed with a dispersant and a dispersion medium, or a yellow light emitting dopant and a blue light emitting dopant selected from a host compound, a dye, a dye and a metal complex are mixed with the dispersant and a dispersion medium.

In the case of white light emission, a method of manufacturing by three primary colors such as red, green, and blue, and a method of manufacturing by complementary colors of yellow and blue are possible.

First, in the case of white light emission by three primary colors, blue light emitting nanoparticles (consist of blue light emitting dopant + host), green light emitting nanoparticles (consisting of green light emitting dopant + host), and red light emitting nanoparticles (red light emitting dopant +) Consisting of a host) can be individually mixed by a predetermined ratio to exhibit white light emission, and white doped nanoparticles can also be prepared by doping the dopant compound corresponding to the RGB three primary colors to the host material at once. .

In the case of white light emission using a complementary color relationship, blue light emitting nanoparticles and yellow light emitting nanoparticles may be separately prepared and then mixed at a predetermined ratio, or white and light emitting nanoparticles may be prepared by doping a blue and yellow dopant to a host material. have.

As the particles become smaller on a nano scale, the specific surface area is increased, and the particles are easily agglomerated by collisions between particles due to Brownian motion in the solution, so that secondary particles are easily formed or precipitated.

In particular, when the fine particles are manufactured using a metal complex having a high specific gravity, precipitation phenomenon due to the instability of the fine particles is accelerated.

In addition, the fine particles have a lot of defects on the surface during the manufacturing process, such defects cause a low luminous efficiency.

The present inventors have conducted research to improve the stability of the nanoparticles, as a result of using a dispersant in the manufacturing process of the nanoparticles to solve the above-described problems, the production of white light emitting nanoparticles with excellent dispersion stability and excellent luminous efficiency It confirmed and completed this invention.

The nanoparticle dispersion of the present invention may further include a cationic dispersant, an anionic dispersant, a cationic anionic dispersant, a nonionic dispersant, or a polymer dispersant.

Cationic dispersants, anionic dispersants and cationic anionic dispersants used herein impart charge to the surface of the nanoparticles, thereby imparting stability to the particles by repulsive forces between charges. The nonionic dispersing agent and the polymer dispersing agent are coated on the surface of the particles to have stability in the dispersion due to the steric effect by entropy repulsion between the adsorbing polymers and the penetration pressure effect between the particles.

The polymer adsorbed at the particle interface maintains a very stable random coil structure determined by the entropy balance with the dispersion medium. In addition, when the nanoparticles adsorbing the polymer layer on the interface are close to each other, the concentration of the polymer becomes high at the contact portion, and consequently, the inflow pressure promotes the inflow of the dispersion medium, thereby contributing to the safety of the particles in the dispersion.

The white light emitting nanoparticles for forming a light-emitting body of the organic photoelectric device of the present invention includes a host and a dopant together with a dispersant as described above.

Generally, the evaluation criteria of the organic compound for organic photoelectric device have high luminous quantum efficiency, good film forming property, and high carrier transporting property. The host has low self-luminous ability but film forming property. It is a matrix material in which these high and high luminous ability materials are mixed.

The material used as the host has the property of injecting electrons or holes, having good film forming property, high heat resistance, high excitation energy level, excellent charge mobility, and light emission spectrum overlapping the dopant absorption spectrum. The energy gap between Homo and Lumo must be wide. As a kind of compound which satisfies these properties, an aromatic monocyclic compound, an aromatic condensed ring compound, a hetero monocyclic compound, a heterocondensed ring compound, a metal complex, a pi conjugated polymer compound, a cis conjugated polymer compound, an amine derivative, steel Bene compounds, hydrazone compounds and the like.

In the present invention, as a host material satisfying such properties, 4,4'-Bis (carbazol-9-yl) biphenyl (CBP), 4,4'-Bis (9-carbazo-lyl) -2,2 '-dimethyl-biphenyl (CDBP), 4,4', 4 "-tri (N-carbazolyl) triphenylamine (TCTA), 2,9-dimethyl-4,7-diphenyl-phenanthroline (BCP), 9,10-bis (4- (N-carbazolyl) phenyl) anthracene (BCPA), 3- (biphenyl-4-yl) -4-phenyl-5 (4-tert-butylphenyl) -1,2,4-triazole (TAZ), 1 , 1-Bis (4-bis (4-methylphenyl) -aminophenyl) -cyclohexane (TAPC), Tris- (8-hydroxyquinolone) aluminum (Alq ₃ ), metal phthalocyanine, 4-biphenyloxolato aluminum (III) bis (2-methyl -8-quinolinato) 4-phenylphenolate (BAlq), N, N'-Bis (3-methylphenyl) -N, N'-diphenylbenzidine (TPD), 4,4'-bis {N- (1-naphthyl) -N -phenyl-amino} biphenyl ( α -NPD), N- (4-((1E) -2- (10- (4- (diphenylamino) styryl) anthracene-9-yl) vinyl) phenyl) -N-phenylbenzeneamine ( BSA-2), 4,4'-bis (2,2'diphenylvinyl) -1,1'-biphenyl (DPVBi), 2-tert-butylphenyl-5-biphenyl-1,3,4-oxadiazole (PBD), poly (vinylcarbazole) (PVK) and its derivatives, carbazole substituted polyacet ylenes (PAC), poly ( p -phenylene vinylene) (PPV) and derivatives thereof, poly [2-methoxy-5- (2'-ethylhexyloxy) -1,4-phenylenevinylene-co-4,4'-bisphenylenevinylene] ( MEH-BP-PPV), poly (thiophene) (PAT) and derivatives thereof, poly (9,9'-dialkylfluorene) (PDAF) and derivatives thereof, poly ( p -phenylene) (PPP) and derivatives thereof, poly (1 One or more of, 4-naphthalene vinylene) (PNV) and its derivatives, polystyrene (PS) and its derivatives, polysilane and its derivatives, poly (arylenevinylene) (PAV) and its derivatives are selected and used.

A dopant is a guest or dopant because it is a compound having a high luminescence ability and used in a small amount in a host.

The dopant is a substance that is doped into the host to emit light. In the present invention, a dopant is selected from a dye, a dye, and a metal complex.

Types of dyes or dyes used as dopants in the present invention include aromatic monocyclic compounds such as benzidine, benzene derivatives, biphenyl derivatives, anthracene and derivatives thereof, tetracene and derivatives thereof, pyrene and derivatives thereof, phenylene and Aromatic condensed cyclic compounds such as derivatives thereof, coronene, etc., 5,5 "-bis {4- [bis (4-methylphenyl) amino] phenyl} -2-2 ': 5', 2" -terthiophene ( Heterocyclic compounds such as BMA-3T), oxadiazole-based compounds, pyranic DCM (4- (Dicyanomethylene) -2-methyl-6- (4-dimethlaminostyryl) -4H-pyran), cumarins and derivatives thereof, Heterocondensed ring compounds such as nired, quinacridone and derivatives thereof, carbazole and derivatives thereof, styryl compounds such as TPB (1,1,4,4-Tetraphenyl-1,3-butadiene), Carbonylated compounds such as stilbene compounds, azobenzene compounds, xanthenes, rhodamines, etc. There are Surgical Ara phosphorus compounds, fluorene and derivatives thereof, such as alkylene indigo-based compound, such as water, indigo (indigo, BIS-OH.

As a specific kind of the dye or dye used as the dopant in the present invention, one or two or more compounds selected from Formula 1 below may be used.

<Formula 1>

In the present invention, the metal complex used as the dopant is specifically the following Structural Formulas 1 to 4, and one or two or more metal complexes selected from these were used as the dopant.

<Structure 1>

<Formula 2>

In Formula 1 and Formula 2, M represents Europium, Terbium, Cerium, or Tulium,

n ₁ is an integer from 2 to 3, n ₂ is an integer from 1 to 3, n ₃ is an integer from 0 to 3,

X represents a hydrogen or deuterium element, Y has the same or different C ₁ -C ₂₀ groups, a hydroxyl group, a nitro group, a sulfonyl group, a cyano group, a trichloromethyl group, a sulfonic acid group, a phosphoric acid group, a substituent Aryl ring group, nitrogen, oxygen, sulfur, silicon may have one of the hetero-ventilation, silyl group, diazo group, mercapto group which may have a substituent containing one,

L is an aryl ring which may have a substituent, a heteroaryl ring which may have a substituent, phenanthroline, a phosphon oxide including an aryl ring which may have a substituent, a sulfoxide including an aryl ring which may have a substituent, Or a diphosphon oxide containing an aryl ring which may have a substituent.

<Structure 3>

　

(In Structural Formula 3, n = 1 or 2 or 3 and a and b are each independently 0 (pentagon ring) or 1 (hexagon ring).

The ring of formula 3 is each a ring containing a double bond or consisting of a single bond, preferably an aromatic ring.

M is a metal atom forming an octahedral complex, in particular iridium;

L is a bidentate ligand of a monovalent anion coordinated to M via sp ² carbon and a heteroatom, or a bidentate ligand coordinated via a non-covalent electron pair of a heteroatom and a heteroatom of a monovalent anion, for example Is a ligand.

<Formula 2>

Y ¹ is a monodentate ligand coordinated via a non-covalent electron pair of heteroatoms, and Y ² is a monodentate ligand coordinated with a nitrogen atom of sp ² carbon and monovalent anion.

In Formula 3, X ¹ to X ⁸ each represent a carbon atom or a hetero atom, and when any one of X ¹ to X ⁸ represents a carbon atom, R ¹ to R ⁸ bonded to X ¹ to X ⁸ representing a carbon atom Each represents a substituent bonded to the carbon atom.

X ¹ to X ⁸ When any one of these represents a nitrogen, oxygen or sulfur atom, R ¹ to R ⁸ bonded to X ¹ to X ⁸ each represent a non-covalent electron pair, and the substituents represented by R ¹ to R ⁸ may form a ring. .

Substituents represented by R ¹ to R ⁸ are each independently a hydrogen atom, a substituted or unsubstituted aryl group having 6 or more carbon atoms, a substituted or unsubstituted heteroaryl group having 2 or more carbon atoms, a substituted or unsubstituted alkyl group having 1 or more carbon atoms, Substituted or unsubstituted C2 or more amino group, substituted or unsubstituted C1 or more alkoxy group, halogen atom, nitro group, substituted or unsubstituted C6 or more arylene group, substituted or unsubstituted C2 or more heteroarylene group , Substituted or unsubstituted C1 or more alkylene group.

<Structure 4>

In Formula 4, M represents platinum, and A, B, C, and D represent a nitrogen-containing hetero ring in which any two may have a substituent and the other two represent an aryl ring or hetero ring which may have a substituent. Or A, B, C and D all represent a nitrogen-containing hetero ring which may have a substituent,

S ₁ , S ₂ , S ₃ , S ₄ represent oxygen, sulfur, a divalent substituent or a methylene chain.

The rare earth metal complex represented by Formula 1 or Formula 2 specifically includes Tris (dibenzoylmethane) mono (phenanthroline) europium (III) {Eu (DBM) ₃ Phen}, Tris (dibenzoylmethane) mono (triphenylphosphineoxide) europium (III) { Eu (DBM) ₃ TPPO, Tris (4,4,4-trifluoro-1- (2-thylenil-1,3-butanedionanion) mono (phenanthroline) europium (III) {Eu (TTA) ₃ Phen}, Tris (biphenoylmethane ) mono (phenanthroline) europium (III) {Eu (BDBBM) ₃ Phen}, Tris (dinaphthoylmethane) mono (phenanthroline) europium (III) {Eu (DNM) ₃ Phen}, Tris (di (4-bromo) benzoylmethane) mono (phenanthroline) europium (III) {Eu (DBrBM) ₃ Phen}, Tris (dibenzoylmethane) mono (5-amonophenanthroline) europium (III) {Eu (DBM) ₃ NH-Phen}, Tris (dibenzoylmethane) mono (4,7 -diphenylphenanthroline) europium (III) {Eu (DBM) ₃ DP-Phen}, Tris (dibenzoylmethane) mono (4,7-dimethylphenanthroline) europium (III) {Eu (DBM) ₃ DM-Phen}, Tris (benzoylacetonato) mono (phenanthroline) europium (III) {Eu (BA) ₃ Phen}, Tris (dibenzoylmethane) mono (phenant hroline) terbium (III) {Tb (DBM) ₃ Phen}, Tris (dibenzoylmethane) mono (phenanthroline) cerium (III) {Ce (DBM) ₃ Phen}, Tris (dibenzoylmethane) mono (phenanthroline) thulium (III) {Tm (DBM) ₃ Phen}, Tris (dibenzoylmethane) mono (phenanthroline) terbium (III) {Tb (DBM) ₃ Phen}, Tris (acetylacetonate) terbium (III) {Tb (acac) ₃ }.

Specifically, the iridium metal complex represented by Structural Formula 3 includes Iridium (III) bis (2-phenylpyridinato- N, C ^{2 ′} ) acetylacetonate {Ir ( ppy ) ₂ (acac)} and Iridium (III) bis (2- (4-toly) pyridinato- N, C ^{2 '} ) acetylacetonate {Ir ( tpy ) ₂ (acac)}, Iridium (III) bis (7,8-benzoquinolinato- N, C ^3' ) acetylacetonate {Ir ( bzq ) ₂ (acac)}, Iridium (III) bis (2-phenylbenzothiozolato- N, C ^{2 '} ) acetylacetonate {Ir ( bt ) ₂ (acac)}, Iridium (III) bis (2-phenylbenzothiozolato- N, C ^{2 '} ) picolinate {Ir ( bt ) ₂ (pico)}, Iridium (III) bis (2-phenylbenzothiozolato- N, C ^2' ) ( N -methylsalicylimine- N, O ) {Ir ( bt ) ₂ (sal)}, Iridium (III) bis (2- (1-naphthly) benzothiazolate- N, C ^{2 '} ) acetylacetonate {Ir ( bsn ) ₂ (acac)}, Iridium (III) bis (2-phenylquinolyl- N, C ^2' ) acetylacetonate {Ir ( pq ) ₂ (acac)}, Iridium (III) fac -tris (2-phenylpyridinato- N, C ^{2 '} ) { fac -Ir ( ppy ) ₃ }, Iridium (III) fac -tris (7,8 -benzoquinolinate- N, C ^{3 '} ) { fac -Ir ( bzq ) ₃ }, Iridium (III) bis (4,6-di-fluorophenyl)-pyridinato N, C ^{2 '} ) acetylacetonate {FIr (acac)}, Iridium (III) bis (4,6-di-fluorophenyl) -pyridinato- N, C ^2' ) picolinate {FIrpic}, Iridium (III) tris (1 -phenylisoquinoline) {Ir (piq) ₃ }, Iridium (III) tris (2- (4-tolyl) pyridinato- N, C2 ' {Ir (tpy) ₃ }, Iridium (III) bis (dibenzo [f, h] quinoxaline) acetylacetonate {Ir (DBQ) ₂ (acac)}, Iridium (III) bis (1-phenylisoquinolinyl- N, C ^{2 '} ) acetylacetonate {Ir ( piq ) ₂ (acac)}.

Specifically, the platinum metal complex represented by Structural Formula 4 is 2,3,7,8,12,12,17,18-octaethly-21H, 23H-porphine platinum (II) (PtOEP), cis- bis [2- (2-thienyl) pyridine-NC ³ ] platinum (II) (Pt (thpy) ₂ ), platinum (II) 2,8,12,17-tetraethly-3,7,13,18-tetramenthly porphyrin (PtOX), platinum (II) and the like.

Advantages and features of the present invention and methods for achieving them will be apparent with reference to the embodiments described below in detail with the accompanying drawings. However, the present invention is not limited to the embodiments disclosed below, but may be implemented in various different forms, only the present embodiments to make the disclosure of the present invention complete, and common knowledge in the art to which the present invention pertains. It is provided to fully inform the person having the scope of the invention, which is defined only by the scope of the claims. Like reference numerals refer to like elements throughout.

The white light emitting nanoparticles for an organic photoelectric device according to the present invention have a weight ratio of 0.1: 1 to 10000 in order to prevent the exciton disappearance caused by the collision of nanoparticles with the efficient energy transfer from the host to the dopant. It is desirable to have a range of 1: 1.

The dispersion of the white light emitting nanoparticles for the organic photoelectric device of the present invention has a size of about nanoscale (1 ~ 1,000nm), and can be used to prepare the vacuum deposition method, melt detection method, reprecipitation method, etc., vacuum deposition method and melt detection method is a high temperature Since heating conditions are involved, the present invention does not undergo a high temperature process, so there is no degradation due to temperature, and the manufacturing process is produced by a relatively simple reprecipitation method (Japanese Patent Laid-Open No. 6-79168).

A process for producing white light emitting nanoparticles for an organic photoelectric device of the present invention by reprecipitaion will be described below.

First, the dye, dye or metal complex compound used as the dopant is dissolved in a soluble solvent.

Soluble solvents are those that can completely dissolve the dyes, dyes or metal complexes used as dopants and are infinitely dilutable with insoluble solvents, which will be described later. Specifically, such as acetone, tetrahydrofuran, en-methyl pyrrolidone And lower alcohols having 4 or less carbon atoms such as amide solvents, methanol, and ethanol.

At this time, the concentration of the dopant solution in which the dye, dye or metal complex is dissolved is preferably in the concentration range of 1 × 10 ^-7 ~ 10M, to prepare a sufficient amount of the microcrystalline without concentration saturation.

Next, the host compound is added to and dissolved in the metal complex solution prepared as described above.

In this case, the amount of the host compound added is preferably in the range of 0.1: 1 kPa to 10000: 1 of the host: dopant based on the weight ratio, which is an exciton due to the effective energy transfer from the host to the dopant and the collision of the nanoparticles. This is to prevent extinction.

In this case, a dispersant may be used to increase stability of the host-metal complex dopant nanoparticles, to control the generation of secondary particles, and to improve luminous efficiency by removing defects on the surface of the host-metal complex dopant nanoparticles. Add more.

In this case, the dispersant used may include a cationic dispersant, an anionic dispersant, a cationic anionic dispersant, a nonionic dispersant, or a polymer dispersant, all of which are added in the range of 0.001-50 wt% in the total composition. .

The amount of the dispersant as described above is in the range in consideration of aggregation of nanoparticles, thin film formation of nanoparticles, and light emission characteristics.

Cationic dispersants include quaternary ammonium salts, aliphatic amines, alkoxypolyamines, aliphatic amine polyglycol ethers, diamines and polyamines derived from aliphatic amines and aliphatic alcohols.

Anionic dispersants include fatty acid salts, alkyl polyphosphate ester salts, alkyl sulfate ester salts, alkyl aryl sulfonates, aryl sulphate ester salts, acyl methyl tauryl salts, alkyl phosphate ester salts, aryl phosphate ester salts, aryl sulfonic acid formalin condensation. Water, polyoxyethylene alkyl sulfate ester salts, and the like.

Cationic anionic dispersants are compounds in which the cationic structure of the cationic dispersant described above and the anionic structure of the anionic dispersant are contained in one molecule.

Examples of the nonionic dispersant include polyoxyethylene fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkylamines, polyoxyalkylarylamines, polyoxyreylene fatty acid esters, glycerin fatty acid esters, and sorbitan. Fatty acid esters, polyoxyethylene sorbitan fatty acid esters, and the like.

Polymeric dispersants include alkyl hydroxycellulose, cellulose derivatives, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylates and derivatives thereof, polyvinyl alcohol and vinyl acetate copolymers, polyethylene glycol, polypropylene glycol, polyethylene oxide, polycarbonate And polyvinyl methyl ether, polyacrylamide, polyimide, polyarylamine salt polyethylene oxy-polypropylene oxide copolymer, polyacrylate, condensed arylene sulfonate, polyvinyl sulfate, styrene-acrylate copolymer and the like.

Next, a solution in which the metal complex and the host compound are dissolved in the soluble solvent as described above is introduced into a strongly insoluble solvent that is strongly stirred using a micro-syringe.

The insoluble solvent used here is a solvent which is insoluble in the dopant metal complex and the host compound or has a low solubility of 1.0 × 10 ⁻¹ g / L or less and is infinitely dilutable with the soluble solvent.

Specific examples of insoluble solvents include water (H ₂ O), cyclohexane, decalin, lower alcohols having 4 or less carbon atoms, and the like.

As such, when the solution in which the metal complex dopant compound and the host compound are dissolved is injected into a strongly stirred insoluble solvent, the doped host-metal complex compound is reprecipitated in a form in which it is precipitated while meeting an insoluble solvent. (reprecipitation).

At this time, the size of the precipitated particles is nano-scale, that is, very fine as having a diameter of 1 ~ 1,000nm. The nanoscale multicomponent nanoparticles prepared by the reprecipitation method simultaneously contain the host and dopant, and are in spatial contact with each other. It is influenced by the distance of the dopant emitting light. In the case of multicomponent nanoparticles, the excitons of the Zhohost within the nanoscale matrix are efficiently delivered to the Zodopant in post energy transfer or dex energy transfer mechanisms, ultimately increasing luminous efficiency. In addition, since the light emitter is a nanoparticle, the specific surface area per unit is increased to easily transfer energy of the host material from the outside. Since the excitons of the excited host materials are efficiently transferred to the dopant, the luminous efficiency is increased as a result. The host matrix of multicomponent nanoparticles acts as an antenna for energy harvesting and effectively delivers excitons to dopants. In addition, multi-component light emitting nanoparticles exhibit high luminous efficiency even at low concentrations of dopants, which can prevent self-quenching.

The multi-component light emitting nanoparticles according to the present invention can be used as a material for forming various light emitting sources and lighting devices by being added to display devices and displays as well as light emitting materials for optoelectronic devices. For example, it may be used as a light emitting material such as a backlight light source of a liquid crystal display device, home lighting, interior lighting, street lighting.

Hereinafter, the light emitting efficiency is very excellent when the light emitting compound for an organic photoelectric device according to the embodiments of the present invention is described with reference to specific embodiments. However, the content not described herein is omitted because it can be inferred technically sufficient by those skilled in the art.

1. Preparation of red (R), green (G), blue (B) light-emitting nanoparticle dispersions

< Example  1>

1.0 mg of Iridium (III) bis (1-phenylisoquinolinyl- N, C ^{2 '} ) acetylacetonate (hereinafter Ir (piq) ₂ (acac)), an iridium-based metal complex, was dissolved in 30 mL of soluble solvent tetrahydrofuran and irradiated with 0.05 mM Ir. After preparing the (piq) ₂ (acac) solution, 58 mg of the host material PVK was dissolved therein to prepare an Ir (piq) ₂ (acac) -PVK tetrahydrofuran mixed solution.

Then, 0.5 mL of a 5.0 wt% aqueous polyvinyl alcohol solution was injected into 9.5 mL of an insoluble solvent (H ₂ O), which was strongly stirred, and then Ir (piq) using a 500 μL micro syringe. ₂₀₀ uL of a ₂ (acac) -PVK tetrahydrofuran mixed solution was injected to obtain a red light-emitting nanoparticle dispersion.

< Example 2>

Green luminescent nanoparticle dispersions were prepared using 1.0 mg of Iridium (III) bis (2-phenylpyridinato- N, C ^{2 ′} ) acetylacetonate (hereinafter Ir (ppy) ₂ (acac)) in the same manner as in Example 1.

< Example  3>

Blue luminescent nanoparticle dispersions and blue luminescent nanoparticle films were prepared using 0.38 mg of perylene in the same manner as in Example 1.

2. Preparation of white light emitting nanoparticle dispersion and white light emitting nanoparticle film by R-G-B mixing

< Example  4>

3 mL of the red luminescent nanoparticle dispersion prepared in Example 1, 2 mL of the green luminescent nanoparticle dispersion prepared in Example 2, and 4 mL of the blue luminescent nanoparticle dispersion prepared in Example 3 were mixed to prepare a white luminescent nanoparticle dispersion. Prepared.

0.4 mL of 9 mL of the white luminescent nanoparticle dispersion thus prepared was taken and dried using a membrane filter paper having a diameter of 100 nm for 12 hours or more using a filtration and vacuum pump to prepare a white luminescent nanoparticle membrane.

1 is an electron micrograph of the white light emitting nanoparticles prepared in Example 4. FIG.

< Example  5>

Ir (piq) ₂ (acac) 0.26 mg (red luminescent dopant), Ir (ppy) ₂ (acac) 0.50 mg (green luminescent dopant) and perylene 0.38 mg (blue) were dissolved in 30 mL of tetrahydrofuran and 0.012 mM Ir (piq) ₂ (acac), 0.025 mM Ir (ppy) ₂ (acac), and 0.050 mM perylene mixed solution were prepared. 58 mg of host material PVK was dissolved therein.

Thereafter, 0.5 mL of a 5.0 wt% aqueous polyvinyl alcohol solution was injected into 9.5 mL of insoluble solvent (H ₂ O), which was strongly stirred, and then, red, green, and 500 mL micro syringes were used. 200 μL of a tetrahydrofuran solution containing blue dopant and PVK was injected to obtain a white light emitting nanoparticle dispersion.

0.4 mL of 10 mL of the white luminescent nanoparticle dispersion thus prepared was taken and dried using a membrane filter paper having a diameter of 100 nm for 12 hours or more using a filtration and vacuum pump to prepare a white luminescent nanoparticle membrane.

2 is an electron micrograph of the white light emitting nanoparticles prepared in Example 5. FIG.

3. Preparation of Yellow Light Emitting Nanoparticle Dispersion

< Example  6>

Yellow luminescent nanoparticle dispersion and yellow luminescence using 0.23 mg of 4- (Dicyanomethylene) -2-methyl-6- (4-dimethlaminostyryl) -4H-pyran (hereinafter DCM, yellow luminescent dopant) in the same manner as in Example 1 Nanoparticle membranes were prepared.

4. Preparation of White Light Emitting Nanoparticle Dispersion and White Light Emitting Nanoparticle Membrane by Complementary Color Mixing

< Example  7>

10 mL of the blue light emitting nanoparticle dispersion prepared in Example 3 and 7 mL of the yellow light emitting nanoparticle dispersion prepared in Example 6 were mixed to prepare a white light emitting nanoparticle dispersion.

0.4 mL of 10 mL of the white luminescent nanoparticle dispersion thus prepared was taken and dried using a membrane filter paper having a diameter of 100 nm for 12 hours or more using a filtration and vacuum pump to prepare a white luminescent nanoparticle membrane.

3 is an electron micrograph of the white light emitting nanoparticles prepared in Example 7. FIG.

< Example  8>

0.1 mg DCM and 0.15 mg perylene were dissolved in 30 mL of tetrahydrofuran, a soluble solvent, to prepare a 0.01 mM DCM solution and a 0.02 mM perylene mixed solution.

58 mg of host material PVK was dissolved therein.

Thereafter, 0.5 mL of a 5.0 wt% aqueous polyvinyl alcohol solution was injected into 9.5 mL of an insoluble solvent (H ₂ O) that was strongly stirred, and then yellow and blue color was obtained using a 500 μL micro syringe. 200 uL of a tetrahydrofuran solution in which dopant and PVK were dissolved was injected to obtain a white light emitting nanoparticle dispersion. 0.4 mL of 10 mL of the white luminescent nanoparticle dispersion thus prepared was taken and dried using a membrane filter paper having a diameter of 100 nm for 12 hours or more using a filtration and vacuum pump to prepare a white luminescent nanoparticle membrane.

4 is an electron micrograph of the white light emitting nanoparticles prepared in Example 8. FIG.

< Comparative example  1>

In the same manner as in Example 8, a white luminescent nanoparticle dispersion liquid and a dispersion film were prepared using 10 mL of water (H ₂ O), which is an insoluble solvent containing no dispersant.

5. OLED  Manufacture of device

< Example  9>

The white light emitting element (element A) was manufactured using the white light emitting nanoparticle dispersion liquid obtained in Example 5. The glass substrate coated with the transparent electrode ITO thin film (20Ω) was ultrasonically cleaned with deionized water, and washed sequentially with acetone and isopropanol.

Thereafter, UV ozone washing was used for 15 µm. The PEDOT / PSS was spin-coated to 500 mW on the ITO electrode to form a common layer, and the light emitting layer was formed by spin coating the white nanoparticles synthesized on the common layer to a thickness of 700 mW.

BAlq was vacuum deposited at 50 kPa as a hole blocking layer on the spin-coated light emitting layer, and Alq3 was deposited at 200 kPa as an electron transporting layer on the hole blocking layer. LiF was deposited on the electron transport layer at 10 kV to form an electron injection layer, and Al was vacuum deposited on the electron injection layer to form a cathode at a thickness of 1500 kV to prepare an organic light emitting diode.

< Comparative example  2>

It proceeded to the same device structure as the white light emitting device manufactured by Example 9. However, white nanoparticles are subtracted from the white light emitting layer, PVK is used as a host compound, and Ir (piq) ₂ (acac), Ir (ppy) 2 (acac) and perylene are mixed together as a dopant compound, which is the same as the white nanoparticle device. The light emitting layer was formed by spin coating to a thickness of 700Å, and the light emission color coordinates were adjusted in the same manner as the light emitting device using the white light emitting nanoparticles and then compared.

5. Analysis of Electron Micrographs

1 is an electron micrograph of a film of white light-emitting nanoparticles in which red, green, and blue light emitting particles prepared in Example 4 are mixed, and FIG. 2 is a dopant of three components prepared in Example 5. Electron micrographs of doped white luminescent nanoparticles.

FIG. 3 is an electron micrograph of luminescent nanoparticles mixed with yellow and blue luminescent particles prepared by Example 7, and FIG. 4 is a white luminescent nanoparticle doped with dopants of two components prepared by Example 8. As electron micrographs of the particles, it can be seen that particles having a nanoscale size of 1 μm or less are uniformly distributed.

6. Evaluation of physical properties

(1) Observation of emission spectrum

The white light emitting nanoparticle dispersion prepared above was measured for emission spectra at an excitation wavelength of 280 nm using a Hitachi F-2500 Spectrophotometer.

5 is a graph showing emission spectra of the white light emitting nanoparticle dispersions of Examples 4, 5, 7, and 8, and FIG. 6 is a graph showing results of emission spectrum measurement of the white light emitting nanoparticle films of Example 8 and Comparative Example 1. FIG. .

(2) Measurement of luminescence intensity

The light emitting nanoparticle dispersion films prepared in Examples 1 to 8 were placed under an ultraviolet lamp having a wavelength of 365 nm and photographed using a digital camera.

7 is a light intensity measurement results for the red, green, blue and white light emitting nanoparticles prepared in Examples 1 to 5, Figure 8 is a yellow and white white light emitting nanoparticles prepared in Examples 6-8 It is the result of measuring the intensity of light.

7. Analysis of the results

The emission spectra of the white light emitting nanoparticle dispersions prepared in Examples 4, 5, 7, and 8 of FIG. 5 are shown. White luminescent nanoparticle dispersions were prepared using blue at 450 nm, green at 520 nm and red at 620 nm. In addition, white light-emitting nanoparticles were produced using yellow near 560 nm and red at 450 nm. In the present invention, the white light emission by the nanoparticles is dispersed in a molecular state in a known vacuum deposition method or a polymer matrix, and thus, compared to the white manufacturing method, the manufacturing process is very simple and the color coordinate can be controlled by a simple mixing ratio. Have

Figure 6 shows the emission spectrum of the white nanoparticle dispersion film prepared by Example 8 and Comparative Example 1. When using a dispersant, compared with the case where no dispersant was used, very high luminous efficiency was shown.

This dispersant is uniformly distributed on the surface of the nanoparticles to prevent secondary aggregation between the nanoparticles to prevent quenching between the nanoparticles resulting in increased luminous efficiency.

In addition, the use of a dispersant increases the luminous efficiency of the overall multicomponent nanoparticles by removing defects generated on the surface of the nanoparticles.

7 and 8 illustrate the light emitted from each nanoparticle by dispersing the red, yellow, green and blue light emitting nanoparticles prepared in Examples 1-8 and the white nanoparticle dispersion film under an ultraviolet lamp having a wavelength of 365 nm. The picture was taken with a digital camera. It can be seen that white light-emitting nanoparticles are also produced by simple mixing of red, green and blue nanoparticles or simple mixing of yellow and blue, or using red, green and blue or yellow and blue dopants.

The light emission color coordinates of the device prepared using the white light emitting nanoparticles prepared by Example 9 was (0.34, 0.35), the luminous efficiency was 1.01 lm / W at 10 mA / cm ² , and the prepared by Comparative Example 2 The luminous efficiency of the comparative device was found to be 0.9 lm / W at 10 mA / cm ² .

This is because the light emitting layer is formed of white light emitting nanoparticles, and the dopant and the host are made of very small particles of nano size, thereby showing better luminous efficiency than the conventional one by effective energy transfer.

Although the embodiments of the present invention have been described above with reference to the accompanying drawings and tables, the present invention is not limited to the above embodiments, but may be manufactured in various forms, and common knowledge in the art to which the present invention pertains. Those skilled in the art can understand that the present invention can be implemented in other specific forms without changing the technical spirit or essential features of the present invention. Therefore, it should be understood that the embodiments described above are exemplary in all respects and not restrictive.

By using the white light emitting nanoparticles for the organic photoelectric device according to an embodiment of the present invention to manufacture the light emitting layer of the organic photoelectric device, in particular, the OLED can improve the energy transfer efficiency from the host to the dopant can form a uniform thin film. . This increases the luminous efficiency of the white light emitting device.

Claims (24)

A host compound; A red (R) light emitting nanoparticle dispersion, a green (G) light emitting nanoparticle dispersion, and a blue (B) light emitting nanoparticle, wherein a dopant compound selected from the group consisting of dyes, dyes, and metal complexes is dispersed in a dispersion medium containing a dispersant. As a white light emitting nanoparticle dispersion prepared by mixing the dispersion, The nanoparticle dispersion is white light emitting nanoparticles having a size of 1 to 1000 nm. A host compound; White light emitting nanoparticles prepared by mixing a yellow (Y) light emitting nanoparticle dispersion and a blue (B) light emitting nanoparticle dispersion in which a dopant compound selected from the group consisting of dyes, dyes, and metal complexes is dispersed in a dispersion medium containing a dispersant. As a particle dispersion, The nanoparticle dispersion is white light emitting nanoparticles having a size of 1 to 1000 nm. A host compound; White light emitting nanoparticles prepared by dispersing a mixed dopant compound of a red light emitting dopant compound, a green light emitting dopant compound, and a blue light emitting dopant compound selected from the group consisting of dyes, dyes, and metal complexes in a dispersion medium containing a dispersant. As a particle dispersion, The nanoparticle dispersion is white light emitting nanoparticles having a size of 1 to 1000 nm. A host compound; As a white light emitting nanoparticle dispersion prepared by dispersing a mixed dopant compound of a yellow light emitting dopant compound selected from the group consisting of a dye, a dye, and a metal complex, and a blue light emitting dopant compound in a dispersion medium containing a dispersant, The nanoparticle dispersion is white light emitting nanoparticles having a size of 1 to 1000 nm. The method according to any one of claims 1 to 4, The nanoparticle dispersion liquid white luminescent nanoparticle dispersion, characterized in that further comprising a selected from the group consisting of a cationic dispersant, an anionic dispersant, a cationic anionic dispersant, a nonionic dispersant, and a polymer dispersant. The method of claim 5, wherein The cationic dispersant is a white light emitting nanoparticle dispersion, characterized in that selected from the group consisting of quaternary ammonium salts, aliphatic amines, alkoxypolyamines, aliphatic amine polyglycol ethers, and diamines or polyamines derived from aliphatic amines and aliphatic alcohols. The method of claim 5, wherein The anionic dispersants include fatty acid salts, alkyl polyphosphate ester salts, alkyl sulfate ester salts, alkyl aryl sulfonates, aryl sulphate ester salts, acyl methyl tauryl salts, alkyl phosphate ester salts, aryl phosphate ester salts, aryl sulfonic acid formalin condensation. Water white and polyoxyethylene alkyl sulfate ester salt The white-white light-emitting nanoparticle dispersion liquid characterized by the above-mentioned. The method of claim 5, wherein The cationic anionic dispersant is a white light emitting nanoparticle dispersion, characterized in that the cationic structure and the anionic structure is contained in one molecule. The method of claim 5, The nonionic dispersant is polyoxyethylene fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene alkyl amine, polyoxy alkyl aryl amine, polyoxy reethylene fatty acid ester, glycerin fatty acid ester, sorbitan fatty acid White luminescent nanoparticle dispersion, characterized in that selected from the group consisting of esters, and polyoxyethylene sorbitan fatty acid ester. The method of claim 5, The polymer dispersing agent is alkyl hydroxy cellulose, cellulose derivative, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylate and derivatives thereof, polyvinyl alcohol and vinyl acetate copolymer, polyethylene glycol, polypropylene glycol, polyethylene oxide, polycarbonate , Polyvinyl methyl ether, polyacrylamide, polyimide, polyarylamine salt polyethylene oxy-polypropylene oxide copolymer, polyacrylate, condensed arylene sulfonate, polyvinyl sulfate, and styrene-acrylate copolymer White luminescent nanoparticle dispersion, characterized in that selected from. The method according to any one of claims 1 to 4, The total content of the dispersant is a white light emitting nanoparticle dispersion, characterized in that 0.001 to 50% by weight. The method according to any one of claims 1 to 4, White luminescent nanoparticle dispersion, characterized in that the mixing weight ratio of the host compound and the dopant compound is 0.1: 1 to 10000: 1. The method according to any one of claims 1 to 4, The dye or dye dopant may be an aromatic monocyclic compound, an aromatic aromatic condensed ring compound, a heteromonocyclic compound, a heterocondensed ring compound, a stilbene compound, a styryl compound, an azobenzene compound, or a carbonini compound. White luminescent nanoparticle dispersion, characterized in that at least one selected from the group consisting of indigo-based compound, squaraine-based compound, fluorene and derivatives thereof. The method of claim 13, The dye or dye dopant is specifically white luminescent nanoparticle dispersion, characterized in that selected from the formula (1). <Formula 1>

The method according to any one of claims 1 to 4, The metal complex dopant is a white light emitting nanoparticle dispersion, characterized in that at least one selected from metal complexes represented by the following structural formulas (1) to (4). <Structure 1> 　

<Formula 2> 　

(In the above formula 1 and formula 2, M represents Europium, Terbium, Cerium or Thulium, n ₁ is an integer from 2 to 3, n ₂ is an integer from 1 to 3, n ₃ is an integer from 0 to 3, X represents a hydrogen element or a deuterium element, Y is an aryl ring group which may have the same or different alkyl group, hydroxy group, nitro group, sulfonyl group, cyano group, trifluoromethyl group, sulfonic acid group, phosphoric acid group, substituent having the same or different carbon atoms, nitrogen, oxygen, sulfur , And represents that one of silicon may have one of heteroventilation, silyl, diazo, and mercapto, which may have a substituent containing it, L is an aryl ring which may have a substituent, a heteroaryl ring which may have a substituent, phenanthroline, a phosphon oxide including an aryl ring which may have a substituent, a sulfoxide including an aryl ring which may have a substituent, Or a diphosphon oxide including an aryl ring which may have a substituent.) <Structure 3>

(In Structural Formula 3, n = 1 or 2 or 3 and a and b are each independently 0 (pentagon ring) or 1 (hexagon ring), Each ring of Formula 3 includes a double bond or consists of a single bond, M is a metal atom forming an octahedral complex, L is a bidentate ligand of a monovalent anion coordinated to M via sp ² carbon and a heteroatom, or a bidentate ligand coordinated via a non-covalent electron pair of a heteroatom and a heteroatom of a monovalent anion, Y ¹ is a monodentate ligand coordinated via a lone pair of heteroatoms, Y ² is a monodentate ligand coordinated with the nitrogen atom of sp ² carbon and monovalent anion, X ¹ to X ⁸ each represents a carbon atom or a hetero atom, X ¹ to X ⁸ in the case specified to the shown carbon atom, the R ¹ to R ⁸ are each the carbon atom bonded to X ¹ to X ⁸ represents a carbon atom Represents a substituent bonded to When any of X ¹ to X ⁸ represents a nitrogen, oxygen or sulfur atom, R ¹ to R ⁸ bonded to X ¹ to X ⁸ each represent a non-covalent electron pair, Substituents represented by R ¹ to R ⁸ are each independently a hydrogen atom, a substituted or unsubstituted aryl group having 6 or more carbon atoms, a substituted or unsubstituted heteroaryl group having 2 or more carbon atoms, a substituted or unsubstituted alkyl group having 1 or more carbon atoms, A substituted or unsubstituted C2 or more amino group, a substituted or unsubstituted C1 or more alkoxy group, a halogen atom, or a nitro group, wherein the substituents represented by R ¹ to R ⁸ may form a ring.) <Structure 4>

(In the above formula 4 M represents platinum, any two of A, B, C, D represents a nitrogen-containing hetero ring that may have a substituent and the other two represents an aryl ring or hetero ring that may have a substituent or Or A, B, C and D all represent a nitrogen-containing hetero ring which may have a substituent, S ₁ , S ₂ , S ₃ , and S ₄ each independently represent oxygen, sulfur, a divalent substituent, or a methylene chain.) The method of claim 15, L of the structural formula 3 is white luminescent nanoparticle dispersion, characterized in that selected from the ligand of the formula (2). <Formula 2>

The method of claim 15, The metal complex represented by Formula 1 or Formula 2 is tris (dibenzoylmethane) mono (phenanthroline) europium (III) (Tris (dibenzoylmethane) mono (phenanthroline) europium (III), Eu (DBM) ₃ Phen) , Tris (dibenzoylmethane) mono (triphenylphosphineoxide) europium (III) (tris (dibenzoylmethane) mono (triphenylphosphineoxide) europium (III), Eu (DBM) ₃ TPPO), tris (4,4,4- Trifluoro-1- (2-tylenyl-1,3-butanedione anion) mono (phenanthroline) europium (III) (Tris (4,4,4-trifluoro-1- (2-thylenil- 1,3-butanedionanion) mono (phenanthroline) europium (III), Eu (TTA) ₃ Phen), tris (biphenoylmethane) mono (phenanthroline) uropium (III) (Tris (biphenoylmethane) mono (phenanthroline) europium (III), Eu (BDBBM) ₃ Phen), Tris (Dinaphthoylmethane) Mono (phenanthroline) Europium (III) (Tris (dinaphthoylmethane) mono (phenanthroline) europium (III), Eu (DNM) ₃ Phen ), Tris (di (4-bromo) benzoylmethane) mono (phenanthroline) uropium (III) (Tris (di (4-bro mo) benzoylmethane) mono (phenanthroline) europium (III), Eu (DBrBM) ₃ Phen), tris (dibenzoylmethane) mono (5-aminophenanthroline) uropium (III) (Tris (dibenzoylmethane) mono (5- aminophenanthroline) europium (III), Eu (DBM) ₃ NH-Phen), tris (dibenzoylmethane) mono (4,7-diphenylphenanthroline) uropium (III) (Tris (dibenzoylmethane) mono (4,7) -diphenylphenanthroline) europium (III), Eu (DBM) ₃ DP-Phen), tris (dibenzoylmethane) mono (4,7-dimethylphenanthroline) uropium (III) (Tris (dibenzoylmethane) mono (4,7) -dimethylphenanthroline) europium (III), Eu (DBM) ₃ DM-Phen), tris (benzoylacetonato) mono (phenanthroline) uropium (III) (Tris (benzoylacetonato) mono (phenanthroline) europium (III), Eu (BA) ₃ Phen), Tris (dibenzoylmethane) mono (phenanthroline) terbium (III) (Tris (dibenzoylmethane) mono (phenanthroline) terbium (III), Tb (DBM) ₃ Phen), tris (di Benzoylmethane) mono (phenanthroline) cerium (III) (Tris (dibenzoylmethane) mono (phenanthroline) cerium (III), Ce (DBM) ₃ Phen), Tris (dibenzoylmethane) mono (phenanthroline) tulium (III) (Tris (dibenzoylmethane) mono (phenanthroline) thulium (III), Tm (DBM) ₃ Phen), tris (dibenzoylmethane Mono (phenanthroline) terbium (III) (Tris (dibenzoylmethane) mono (phenanthroline) terbium (III), Tb (DBM) ₃ Phen), and Tris (acetylacetonate) terbium (III) (Tris (acetylacetonate) terbium (III), Tb (acac) ₃ ) White luminescent nanoparticle dispersion, characterized in that selected from the group consisting of. The method of claim 15, Metal complex represented by the above formula 3 is iridium (III) bis (2-phenyl pyridinium Nei Sat - N, C ^{2 ')} acetylacetonate (Iridium (III) bis (2 -phenylpyridinato- N, C 2') acetylacetonate , Ir ( ppy ) ₂ (acac)), iridium (III) bis (2- (4-tolyl) pyridinato- N, C ^{2 '} ) acetylacetonate (Iridium (III) bis (2- (4- toly) pyridinato- N, C ^{2 '} ) acetylacetonate, Ir ( tpy ) ₂ (acac)}, iridium (III) bis (7,8-benzoquinolinate- N, C ^3' ) acetylacetonate (Iridium III) bis (7,8-benzoquinolinato- N, C ^{3 '} ) acetylacetonate, Ir ( bzq ) ₂ (acac)), iridium (III) bis (2-phenylbenzothiazolyto- N, C ^2' ) acetylaceto Nate (Iridium (III) bis (2-phenylbenzothiozolato- N, C ^{2 '} ) acetylacetonate, Ir ( bt ) ₂ (acac)), iridium (III) bis (2-phenylbenzothiazolyto- N, C ^2' ) Picolinate (Iridium (III) bis (2-phenylbenzothiozolato- N, C ^{2 ′} ) picolinate, Ir ( bt ) ₂ (pico)), iridium (III) bis (2-phenylbenzothiazolyto- N, C ^{2 '} ) ( N -methylsalicylmine N, O ) (Iridium (III) bis (2-phenylbenzothiozolato- N, C ^{2 '} ) ( N- methylsalicylimine- N, O ), Ir ( bt ) ₂ (sal)), Iridium (III) bis (2- (1-naphthyl) benzothiazole reyito - N, C ^{2 ')} acetylacetonate (Iridium (III) bis (2- (1-naphthyl) benzothiazolate- N, C 2' 2) acetylacetonate, Ir (bsn) ( acac)), iridium (III) bis (2-phenyl quinolyl nolil - N, C ^{2 ')} acetylacetonate (iridium (III) bis (2 -phenylquinolyl- N, C 2') acetylacetonate, Ir (pq) 2 ( acac)), iridium (III) fac - tris (2-phenyl-pyridinyl Nei Sat ^{- N, C 2 ') (} iridium (III) fac -tris (2-phenylpyridinato- N, C 2'), fac -Ir ( ppy) _3), iridium (III) fac - tris (7,8-benzo quinolinyl carbonate ^{- N, C 3 ') (} iridium (III) fac -tris (7,8-benzoquinolinate- N, C 3'), fac- Ir ( bzq ) ₃ ), iridium (III) bis (4,6-difluorophenyl) -pyridinato- N, C ^{2 ′} ) acetylacetonate (Iridium (III) bis (4,6- ^{difluorophenyl) -pyridinato- N, C 2 '} ) acetylacetonate, FIr (acac)), iridium (III) bis (4,6-di-fluoro-phenyl) -pyrido Digne SAT - N, C ^{2 ')} picolinate (Iridium (III) bis (4,6 -difluorophenyl) -pyridinato- N, C 2') picolinate, FIrpic), Iridium (III) Tris (1-phenyl-isoquinoline) (Iridium (III) tris (1-phenylisoquinoline), Ir (piq) ₃ ), Iridium (III) tris (2- (4-tolyl) pyridinito- N, C ^{2 '} (Iridium (III) tris (2 -(4-tolyl) pyridinato- N, C ^{2 '} , Ir (tpy) ₃ ), iridium (III) bis (dibenzo [f, h] quinoxaline) acetylacetonate (Iridium (III) bis (dibenzo [f , h] quinoxaline) acetylacetonate, Ir (DBQ) ₂ (acac)) and iridium (III) bis (1-phenylisoquinolinyl- N, C ^{2 '} ) acetylacetonate (Iridium (III) bis (1-phenylisoquinolinyl N, C ^{2 '} ) acetylacetonate, Ir ( piq ) ₂ (acac)) white luminescent nanoparticle dispersion, characterized in that selected from the group consisting of. The method of claim 15, The metal complex represented by Structural Formula 4 is 2,3,7,8,12,12,17,18-octaethyl-21H, 23H-phosphine platinum (II) (2,3,7,8,12,12 , 17,18-octaethyl-21H, 23H-porphine platinum (II), PtOEP), cis-bis [2- (2-thienyl) pyridine-NC ³ ] platinum (II) ( cis -bis [2- (2 -thienyl) pyridine-NC ³ ] platinum (II), Pt (thpy) ₂ ), 2,8,12,17-tetraethyl-3,7,13,18-tetramethylporphyrin platinum (II) (2,8 , 12,17-tetraethyl-3,7,13,18-tetramenthyl porphyrin platinum (II), PtOX) and platinum (II) (platinum (II)), characterized in that the white luminescent nanoparticle dispersion . The method according to any one of claims 1 to 4, The host compound is 4,4'-bis (9-carbazolyl) -2,2'-dimethyl-biphenyl (4,4'-Bis (9-carbazolyl) -2,2'-dimethyl-biphenyl, CDBP) , 4,4 ', 4 "-tri (N-carbazolyl) triphenylamine (4,4', 4" -tri (N-carbazolyl) triphenylamine, TCTA), 2,9-dimethyl-4,7-di Phenyl-phenanthroline (2,9-dimethyl-4,7-diphenyl-phenanthroline, BCP), 9,10-bis (4- (N-carbazolyl) phenyl) anthracene (9,10-bis (4- ( N-carbazolyl) phenyl) anthracene, BCPA), 3- (biphenyl-4-yl) -4-phenyl-5 (4-tert-butylphenyl) -1,2,4-triazoleanthracene (3- (biphenyl 4-yl) -4-phenyl-5 (4-tert-butylphenyl) -1,2,4-triazole, TAZ), 1,1-bis (4-bis (4-methylphenyl) -aminophenyl) -cyclo Hexane (1,1-Bis (4-bis (4-methylphenyl) -aminophenyl) -cyclohexane, TAPC), Tris- (8-hydroxyquinolone) aluminum, Alq ₃ ), metal Phthalocyanine, 4-biphenyloxolato aluminum (III) bis (2-methyl-8-quinolinate) 4-phenylphenolate (4-biphenyloxolato aluminum (III) b is (2-methyl-8-quinolinato) 4-phenylphenolate, BAlq), N, N'-bis (3-methylphenyl) -N, N'-diphenylbenzidine (N, N'-Bis (3-methylphenyl)- N, N'-diphenylbenzidine, TPD), 4,4'-bis {N- (1-naphthyl) -N-phenyl-amino} biphenyl (4,4'-bis {N- (1-naphthyl)- N-phenyl-amino} biphenyl, α-NPD), N- (4-((1E) -2- (10- (4- (diphenylamino) styryl) anthracene-9-yl) vinyl) phenyl)- N-phenylbenzeneamine (N- (4-((1E) 2- (10- (4- (diphenylamino) styryl) anthracene-9-yl) vinyl) phenyl) -N-phenylbenzeneamine, BSA-2), 4, 4'-bis (2,2'diphenylvinyl) -1,1'-biphenyl (4,4'-bis (2,2'diphenylvinyl) -1,1'-biphenyl, DPVBi), 2-tert- Butylphenyl-5-biphenyl-1,3,4-oxadiazole (2-tert-butylphenyl-5-biphenyl-1,3,4-oxadiazole, PBD), poly (vinylcarbazole) , PVK) and its derivatives, carbazol-substituted polyacetylene (carbazole substituted polyacetylenes, PAC), poly (p - phenylenevinylene) (poly (p -phenylene vinylene) , PPV) and its derivatives, poly [2-methoxy Oxy-5- (2'-ethylhexyloxy) -1,4-phenylenevinylene -Co-4,4'-bisphenylenevinylene] (poly [2-methoxy-5- (2'-ethylhexyloxy) -1,4-phenylenevinylene-co-4,4'-bisphenylenevinylene], MEH-BP- PPV), poly (thiophene), PAT and derivatives thereof, poly (9,9'-dialkylfluorene) (poly (9,9'-dialkylfluorene), PDAF) and derivatives thereof, poly ( p -phenylene) (poly ( p -phenylene), PPP) and its derivatives, poly (1,4-naphthalene vinylene), PNV) and its derivatives, polystyrene , PS) and derivatives thereof, polysilane and derivatives thereof, poly (arylenevinylene), and PAV and derivatives thereof. A light emitter comprising the white white light emitting nanoparticle dispersion according to any one of claims 1 to 4. An organic photoelectric device comprising the light emitter of claim 21. The method of claim 15, The ring of formula 3 is an aromatic ring white luminescent nanoparticle dispersion. The method according to any one of claims 1 to 4, The white light emitting nanoparticle dispersion, characterized in that the size of the white light emitting nanoparticles 1 to 500 nm.

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