KR102550442B1 - Organic electroluminescent device - Google Patents

Abstract

The present invention relates to an organic electroluminescent device, and can exhibit efficiency and long lifespan characteristics of the device by a dopant-host combination of a light emitting layer in the organic electroluminescent device.
In addition, by providing a dopant-host combination to solve the problems of low efficiency and low lifetime characteristics that occur when using conventional thermally activated delayed fluorescent materials as light emitting materials, the driving voltage is low and the external quantum efficiency (EQE) characteristics are excellent. .

Description

Organic electroluminescent device {Organic electroluminescent device}

The present invention relates to an organic electroluminescent device, and more particularly, to an organic electroluminescent device in which the efficiency and lifetime of the device are improved by a dopant-host combination of an emission layer in the organic electroluminescent device.

Organic light emitting devices (OLEDs) have a simpler structure than other flat panel display devices such as conventional liquid crystal displays (LCDs), plasma display panels (PDPs), and field emission displays (FEDs), and have various advantages in the manufacturing process, It has excellent characteristics of high brightness and viewing angle, fast response speed, and low driving voltage, so it is being actively developed and commercialized to be used as a light source for flat panel displays such as wall-mounted TVs or backlights of displays, lighting, and billboards.

The first organic EL device was reported (C. W. Tang, S. A. Vanslyke, Applied Physics Letters, Volume 51, page 913, 1987) by C. W. Tang of Eastman Kodak, etc. When a voltage is applied, holes injected from the anode and electrons injected from the cathode recombine to form excitons, which are electron-hole pairs, and are converted into light by transferring the energy of the excitons to the light emitting material.

More specifically, the organic light emitting device has a structure including a cathode (electron injection electrode), an anode (hole injection electrode), and one or more organic layers between the two electrodes. At this time, the organic electroluminescent device is a hole injection layer (HIL), a hole transport layer (HTL), a light emitting layer (EML), an electron transport layer (ETL), or an electron transport layer (ETL) from the anode. In order to increase the efficiency of the light emitting layer, a hole transport auxiliary layer or a hole blocking layer (HBL) may be additionally included in front and behind the light emitting layer, respectively.

The light emitting layer is composed of two materials, a host and a dopant, and the dopant should have high quantum efficiency, and the host material preferably has a larger energy gap than the dopant material to facilitate energy transfer to the dopant.

Recently, interest in thermally activated delayed fluorescence (TADF) materials, which are evaluated as materials for 3rd generation OLEDs, following fluorescent materials and phosphorescent materials as light emitting materials, is increasing. The Thermally Activated Delayed Fluorescence (TADF) material is a material that converts a triplet exciton into a singlet, unlike a phosphorescent material that converts a singlet exciton into a triplet and converts into light, and is delayed due to this process. Since it exhibits fluorescence characteristics and can theoretically convert both singlet and triplet excitons into light, 100% internal quantum efficiency is possible, attracting attention as a material that can overcome the limitations of lifespan and efficiency of blue and red phosphorescent materials. Research on this is being actively pursued.

When the above-mentioned Thermally Activated Delayed Fluorescence (TADF) material is used as a light emitting material, the charge separation of molecules is very severe, and when fabricated as a device, the light emitting efficiency of the light emitting body is reduced and the lifespan characteristic is low. There is a problem with indicating

It is necessary to develop a light emitting material capable of improving the above problems and an organic electroluminescent device using the same.

KR 10-1989952 B1

An object of the present invention relates to an organic electroluminescent device, and to provide an organic electroluminescent device having improved efficiency and lifespan of the device by a dopant-host combination of a light emitting layer in the organic electroluminescent device.

Another object of the present invention is to provide a dopant-host combination to solve the problems of reduced efficiency and low lifetime characteristics that occur when using a conventional thermally activated delayed fluorescent material as a light emitting body, so that the driving voltage is low and the external quantum efficiency (EQE) is low. It is to provide an organic electroluminescent device having excellent characteristics.

In order to achieve the above object, the present invention includes a first electrode, a second electrode opposed to the first electrode, and an organic layer disposed between the first electrode and the second electrode, wherein the organic layer includes a light emitting layer, , The light emitting layer includes a host, a first dopant and a second dopant, and the first dopant is an organic compound including a compound represented by Formula 1 or a multimer compound including a compound represented by Formula 1 as a unit structure An electroluminescent device is provided:

[Formula 1]

here,

Ring A, ring B and ring C are the same as or different from each other, and each independently represents a substituted or unsubstituted aryl group having 5 to 30 carbon atoms or a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms,

Z is B or N;

X ₁ and Y ₁ are the same as or different from each other, and are each independently selected from the group consisting of N(R ₁ ), C(R ₂ )(R ₃ ), O and S,

At least one or more X ₁ and Y ₁ are bonded to adjacent A-rings to C-rings to form a ring compound;

R ₁ to R ₃ are the same as or different from each other, and each independently represents hydrogen, heavy hydrogen, a cyano group, a nitro group, a halogen group, a hydroxy group, a substituted or unsubstituted alkylthio group having 1 to 4 carbon atoms, or a substituted or unsubstituted carbon number. Alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted cycloalkyl group having 1 to 20 carbon atoms, substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, substituted or unsubstituted alkynyl group having 2 to 24 carbon atoms, substituted or unsubstituted Aralkyl group having 7 to 30 carbon atoms, substituted or unsubstituted aryl group having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl group having 5 to 60 carbon atoms, substituted or unsubstituted heteroarylalkyl group having 6 to 30 carbon atoms, substituted Or an unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, or a substituted or unsubstituted aralkyl group having 6 to 30 carbon atoms Amino group, substituted or unsubstituted heteroarylamino group having 2 to 24 carbon atoms, substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms and substituted or unsubstituted carbon atoms It is selected from the group consisting of 6 to 30 aryloxy groups, and may combine with adjacent groups to form a substituted or unsubstituted ring.

In the present invention, "hydrogen" is hydrogen, light hydrogen, deuterium or tritium.

In this specification, "halogen group" is fluorine, chlorine, bromine or iodine.

In the present invention, “alkyl” means a monovalent substituent derived from a straight or branched chain saturated hydrocarbon having 1 to 40 carbon atoms. Examples thereof include, but are not limited to, methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, iso-amyl, hexyl, and the like.

In the present invention, “alkenyl” refers to a monovalent substituent derived from a straight-chain or branched unsaturated hydrocarbon having 2 to 40 carbon atoms and having at least one carbon-carbon double bond. Examples thereof include, but are not limited to, vinyl, allyl, isopropenyl, and 2-butenyl.

In the present invention, “alkynyl” refers to a monovalent substituent derived from a straight-chain or branched chain unsaturated hydrocarbon having 2 to 40 carbon atoms and having at least one carbon-carbon triple bond. Examples thereof include, but are not limited to, ethynyl and 2-propynyl.

In the present invention, "alkylthio" means the above-described alkyl group bonded through a sulfur linkage (-S-).

In the present invention, "aryl" means a monovalent substituent derived from an aromatic hydrocarbon having 6 to 60 carbon atoms in a single ring or a combination of two or more rings. In addition, a form in which two or more rings are simply attached to each other (pendant) or condensed may be included. Examples of such aryl include, but are not limited to, phenyl, naphthyl, phenanthryl, anthryl, fluoryl, dimethylfluorenyl, and the like.

In the present invention, “heteroaryl” means a monovalent substituent derived from a monoheterocyclic or polyheterocyclic aromatic hydrocarbon having 6 to 30 carbon atoms. At this time, at least one carbon, preferably 1 to 3 carbons in the ring is substituted with a heteroatom such as N, O, S or Se. In addition, a form in which two or more rings are simply attached to each other or condensed may be included, and furthermore, a form condensed with an aryl group may be included. Examples of such heteroaryl include 6-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, phenoxathienyl, indolizinyl, indolyl ( polycyclic rings such as indolyl, purinyl, quinolyl, benzothiazole, carbazolyl and 2-furanyl, N-imidazolyl, 2-isoxazolyl , 2-pyridinyl, 2-pyrimidinyl and the like, but are not limited thereto.

In the present invention, "aryloxy" is a monovalent substituent represented by RO-, wherein R means an aryl having 6 to 60 carbon atoms. Examples of such aryloxy include, but are not limited to, phenyloxy, naphthyloxy, diphenyloxy, and the like.

In the present invention, "alkyloxy" is a monovalent substituent represented by R'O-, wherein R' means alkyl having 1 to 40 carbon atoms, and has a linear, branched or cyclic structure. can include Examples of alkyloxy include, but are not limited to, methoxy, ethoxy, n-propoxy, 1-propoxy, t-butoxy, n-butoxy, pentoxy, and the like.

In the present invention, “alkoxy” may be straight chain, branched chain or cyclic chain. The number of carbon atoms in alkoxy is not particularly limited, but is preferably 1 to 20 carbon atoms. Specifically, methoxy, ethoxy, n-propoxy, isopropoxy, i-propyloxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, Isopentyloxy, n-hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, benzyloxy, p-methylbenzyloxy, etc. It may be, but is not limited thereto.

As used herein, "aralkyl" refers to an aryl-alkyl group where aryl and alkyl are defined above. Preferred aralkyls include lower alkyl groups. Non-limiting examples of suitable aralkyl groups include benzyl, 2-phenethyl and naphthalenylmethyl. Attachment to the parent moiety is via an alkyl.

In the present invention, "arylamino group" means an amine substituted with an aryl group having 6 to 30 carbon atoms.

In the present invention, "alkylamino group" means an amine substituted with an alkyl group having 1 to 30 carbon atoms.

In the present invention, “aralkylamino group” means an amine substituted with an aryl-alkyl group having 6 to 30 carbon atoms.

In the present invention, "heteroarylamino group" means an amine group substituted with an aryl group having 6 to 30 carbon atoms and a heterocyclic group.

In the present invention, "heteroaralkyl group" means an aryl-alkyl group substituted with a heterocyclic group.

In the present invention, “cycloalkyl” means a monovalent substituent derived from a monocyclic or polycyclic non-aromatic hydrocarbon having 3 to 40 carbon atoms. Examples of such cycloalkyl include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, adamantine, and the like.

In the present invention, “heterocycloalkyl” means a monovalent substituent derived from a non-aromatic hydrocarbon having 3 to 40 carbon atoms, and one or more carbons in the ring, preferably 1 to 3 carbons, are N, O, S or Se is substituted with a heteroatom such as Examples of such heterocycloalkyl include, but are not limited to, morpholine, piperazine, and the like.

In the present invention, “alkylsilyl” refers to silyl substituted with alkyl having 1 to 40 carbon atoms, and “arylsilyl” refers to silyl substituted with aryl having 6 to 60 carbon atoms.

In the present invention, "condensed ring" means a condensed aliphatic ring, a condensed aromatic ring, a condensed heteroaliphatic ring, a condensed heteroaromatic ring, or a combination thereof.

In the present specification, "alicyclic compound" has the same meaning as "aliphatic hydrocarbon ring", and refers to a non-aromatic ring consisting of only carbon and hydrogen atoms.

In the present specification, "heteroalicyclic compound" refers to an alicyclic compound containing at least one heteroatom by replacing one or more carbon atoms of the "aliphatic hydrocarbon ring" with a heteroatom.

Examples of the “aromatic hydrocarbon ring” in the present specification include, but are not limited to, a phenyl group, a naphthyl group, an anthracenyl group, and the like.

In the present specification, "aliphatic heterocycle" means an aliphatic ring containing one or more of heteroatoms.

In the present specification, "aromatic heterocycle" means an aromatic ring containing one or more of heteroatoms.

In the present specification, the aliphatic hydrocarbon ring, aromatic hydrocarbon ring, aliphatic heterocycle, and aromatic heterocycle may be monocyclic or polycyclic.

In the present specification, “concentration quenching” means that the luminous efficiency of a device decreases as the concentration of dopant molecules increases.

In the present specification, “boron-based element”, “boron-based compound”, and “boron-based dopant” refer to a boron (B) element having an atomic number of 5, a compound containing boron, or a dopant.

In this specification, "substitution" means that a hydrogen atom bonded to a carbon atom of a compound is replaced with another substituent, and the position to be substituted is not limited as long as the hydrogen atom is substituted, that is, a position where the substituent can be substituted, and when two or more are substituted , Two or more substituents may be the same as or different from each other. The substituent is hydrogen, a cyano group, a nitro group, a halogen group, a hydroxy group, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 24 carbon atoms, a heteroalkyl group having 2 to 30 carbon atoms, and a C6 to C30 alkenyl group. Aralkyl group of 30, aryl group of 5 to 30 carbon atoms, heteroaryl group of 2 to 30 carbon atoms, heteroarylalkyl group of 3 to 30 carbon atoms, alkoxy group of 1 to 30 carbon atoms, alkylamino group of 1 to 30 carbon atoms, 6 to 30 carbon atoms It may be substituted with one or more substituents selected from the group consisting of an arylamino group of 30, an aralkylamino group of 6 to 30 carbon atoms, and a hetero arylamino group of 2 to 24 carbon atoms, but is not limited to the above examples.

In the present invention, "to form a ring by bonding with adjacent groups" means a substituted or unsubstituted aliphatic hydrocarbon ring by bonding with adjacent groups; A substituted or unsubstituted aromatic hydrocarbon ring; A substituted or unsubstituted aliphatic heterocycle; A substituted or unsubstituted aromatic heterocycle; or to form a condensed ring thereof.

The present invention relates to an organic electroluminescent device in which the efficiency and lifetime of the device are improved by a dopant-host combination of a light emitting layer in the organic electroluminescent device.

In addition, by providing a dopant-host combination to solve the problems of low efficiency and low lifetime characteristics that occur when using conventional thermally activated delayed fluorescent materials as light emitting materials, the driving voltage is low and the external quantum efficiency (EQE) characteristics are excellent. .

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily implement the present invention. However, the present invention may be embodied in many different forms and is not limited to the embodiments described herein.

Delayed fluorescence that can be used in OLED can be divided into two types. The first is the triplet-triplet annihilation (TTA) process. The TTA process was first discovered using pyrene molecules and is also known as p-type delayed fluorescence. A singlet state is formed by interaction or collision of molecules excited in a triplet state. Occurs when high

The second way to utilize the triplet exciton is to utilize the TADF material as mentioned above. The TADF phenomenon utilizes room temperature thermal energy (approximately 28 meV) in a material where the energy difference between the singlet state and the triplet state is extremely small, and the reverse interphase transition from the triplet state to the singlet state with higher energy (Reverse Inter System Crossing; RISC), and as this singlet state transitions to the ground state, delayed fluorescence may be exhibited.

TADF materials require a difference between singlet and triplet energies (Δ E _ST ) should be minimized. Theoretically, in order to obtain a small ΔE _ST , the distribution of molecular orbitals of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) in a molecule must be separated. A common method for separating HOMO and LUMO is to use a donor group and an acceptor group in a molecule and minimize the interaction between these two groups, that is, limit conjugation between donor and acceptor or utilize steric hindrance.

In the case of the Donor-Accepter type luminous body used in the existing thermally activated delayed fluorescence device, the singlet-triplet energy difference was minimized by introducing a substituent that pulls electron density and a substituent that pushes electron density into one molecule in order to use triplet energy. . In the case of a light emitting body introducing this concept, since the charge separation of molecules is very severe and the polarity of molecules increases, the attractive force due to the dipoles between molecules becomes stronger. As a result, the luminous efficiency of the light emitting body is lowered during device manufacturing, and the lifespan is low.

On the other hand, in the case of the boron-based light emitting body used in this patent, since the singlet-triplet energy is minimized through a multiple resonance structure rather than a donor-accepter type, the polarity of the molecule is relatively small, and the attraction of the dipole is relatively weak. Due to this, since it is well dispersed and doped in the host material during device fabrication, the efficiency or lifetime of the device is high.

Specifically, the organic electroluminescent device of the present invention includes a first electrode, a second electrode opposed to the first electrode, and an organic layer disposed between the first electrode and the second electrode, the organic layer including a light emitting layer, , The light-emitting layer may include a host, a first dopant, and a second dopant, and the first dopant may include a compound represented by Formula 1 below or a multimer compound including a compound represented by Formula 1 below in a unit structure. there is:

[Formula 1]

here,

Ring A, ring B and ring C are the same as or different from each other, and each independently represents a substituted or unsubstituted aryl group having 5 to 30 carbon atoms or a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms,

Z is B or N;

X ₁ and Y ₁ are the same as or different from each other, and are each independently selected from the group consisting of N(R ₁ ), C(R ₂ )(R ₃ ), O and S,

At least one or more X ₁ and Y ₁ are bonded to adjacent A-rings to C-rings to form a ring compound;

R ₁ to R ₃ are the same as or different from each other, and each independently represents hydrogen, heavy hydrogen, a cyano group, a nitro group, a halogen group, a hydroxy group, a substituted or unsubstituted alkylthio group having 1 to 4 carbon atoms, or a substituted or unsubstituted carbon number. Alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted cycloalkyl group having 1 to 20 carbon atoms, substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, substituted or unsubstituted alkynyl group having 2 to 24 carbon atoms, substituted or unsubstituted Aralkyl group having 7 to 30 carbon atoms, substituted or unsubstituted aryl group having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl group having 5 to 60 carbon atoms, substituted or unsubstituted heteroarylalkyl group having 6 to 30 carbon atoms, substituted Or an unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, or a substituted or unsubstituted aralkyl group having 6 to 30 carbon atoms Amino group, substituted or unsubstituted heteroarylamino group having 2 to 24 carbon atoms, substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms and substituted or unsubstituted carbon atoms It is selected from the group consisting of 6 to 30 aryloxy groups, and may combine with adjacent groups to form a substituted or unsubstituted ring.

The compound represented by Formula 1 may be a compound represented by Formula 2 below:

[Formula 2]

here,

A, B, Z, X ₁ and Y ₁ are as defined in Formula 1 above,

R ₄ to R ₆ are the same as or different from each other, and each independently represents hydrogen, heavy hydrogen, a cyano group, a nitro group, a halogen group, a hydroxy group, a substituted or unsubstituted alkylthio group having 1 to 4 carbon atoms, or a substituted or unsubstituted carbon number. Alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted cycloalkyl group having 1 to 20 carbon atoms, substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, substituted or unsubstituted alkynyl group having 2 to 24 carbon atoms, substituted or unsubstituted Aralkyl group having 7 to 30 carbon atoms, substituted or unsubstituted aryl group having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl group having 5 to 60 carbon atoms, substituted or unsubstituted heteroarylalkyl group having 6 to 30 carbon atoms, substituted Or an unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, or a substituted or unsubstituted aralkyl group having 6 to 30 carbon atoms Amino group, substituted or unsubstituted heteroarylamino group having 2 to 24 carbon atoms, substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms and substituted or unsubstituted carbon atoms It is selected from the group consisting of 6 to 30 aryloxy groups, and may combine with adjacent groups to form a substituted or unsubstituted ring.

The ring A and ring B may be compounds selected from the group consisting of ring compounds represented by Formulas 3 to 8 below:

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

here,

는 축합되는 부분을 의미하며,

means the condensed part,

n, p, r and t are the same as or different from each other, and each independently represents an integer from 0 to 2,

m, q, s, and u are the same as or different from each other, and each independently represents an integer from 0 to 4;

X ₂ to X ₅ are the same as or different from each other, and are each independently selected from the group consisting of C (R ₁₅ ), N, and Si (R ₁₆ );

X ₆ to X ₁₀ are the same as or different from each other, and are each independently selected from the group consisting of C(R ₁₇ )(R ₁₈ ), N(R ₁₉ ), O, S, and Si(R ₂₀ )(R ₂₁ ); ,

R ₇ to R ₂₁ are the same as or different from each other, and each independently represents hydrogen, heavy hydrogen, a cyano group, a nitro group, a halogen group, a hydroxy group, a substituted or unsubstituted alkylthio group having 1 to 4 carbon atoms, or a substituted or unsubstituted carbon number. Alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted cycloalkyl group having 1 to 20 carbon atoms, substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, substituted or unsubstituted alkynyl group having 2 to 24 carbon atoms, substituted or unsubstituted Aralkyl group having 7 to 30 carbon atoms, substituted or unsubstituted aryl group having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl group having 5 to 60 carbon atoms, substituted or unsubstituted heteroarylalkyl group having 6 to 30 carbon atoms, substituted Or an unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, or a substituted or unsubstituted aralkyl group having 6 to 30 carbon atoms Amino group, substituted or unsubstituted heteroarylamino group having 2 to 24 carbon atoms, substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms and substituted or unsubstituted carbon atoms It is selected from the group consisting of 6 to 30 aryloxy groups, and may combine with adjacent groups to form a substituted or unsubstituted ring.

The Z may be B.

The first dopant exhibits delayed fluorescence characteristics. The first dopant may be included in an amount greater than that of the second dopant in the organic layer. Specifically, the light emitting layer of the organic electroluminescent device of the present invention may include 3 to 50% by weight of the first dopant, 0.5 to 5% by weight of the second dopant, and the rest of the host. When the light emitting layer is formed by mixing the first dopant, the second dopant, and the host within the above range, the singlet-triplet energy is minimized through a multi-resonance structure, so the polarity of the molecule is relatively small and the polarity of the molecule is small. Due to its relatively weak attractive force, it is easily dispersed and doped with the host material during device manufacturing, so that it can exhibit characteristics of high efficiency or lifespan of the device.

Specifically, the first dopant may be selected from the group consisting of the following compounds:

here,

n is an integer from 0 to 5;

R is hydrogen, heavy hydrogen, a cyano group, a nitro group, a halogen group, a hydroxyl group, a substituted or unsubstituted alkylthio group having 1 to 4 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, or a substituted or unsubstituted carbon atom 1 to 20 cycloalkyl groups, substituted or unsubstituted C2-30 alkenyl groups, substituted or unsubstituted C2-24 alkynyl groups, substituted or unsubstituted C7-30 aralkyl groups, substituted or unsubstituted Aryl group having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl group having 5 to 60 carbon atoms, substituted or unsubstituted heteroaryl group having 6 to 30 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, substituted Or an unsubstituted C1-C30 alkylamino group, a substituted or unsubstituted C6-C30 arylamino group, a substituted or unsubstituted C6-C30 aralkylamino group, a substituted or unsubstituted C2-C24 hetero It is selected from the group consisting of an arylamino group, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, and a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, Adjacent groups may combine with each other to form a substituted or unsubstituted ring.

The second dopant exhibits fluorescence characteristics.

The second dopant may be selected from the group consisting of a condensed ring-containing compound, an amino group-containing compound, a styryl group-containing compound, and a boron-containing compound, and the first dopant may be selected as the second dopant. Specifically, a compound having a wide ΔEST among the first dopants may be selected as the second dopant. More specifically, among the first dopants, a compound having a ΔEST of 0.15 eV or more may be selected as the second dopant, but the dopant is not limited to the above example and can exhibit an effect of improving the efficiency or lifespan of a device by using it with the first dopant. All materials can be used without limitation.

Specifically, the second dopant may be selected from the group consisting of the following compounds:

here,

n is an integer from 0 to 5;

R is hydrogen, heavy hydrogen, a cyano group, a nitro group, a halogen group, a hydroxyl group, a substituted or unsubstituted alkylthio group having 1 to 4 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, or a substituted or unsubstituted carbon atom 1 to 20 cycloalkyl groups, substituted or unsubstituted C2-30 alkenyl groups, substituted or unsubstituted C2-24 alkynyl groups, substituted or unsubstituted C7-30 aralkyl groups, substituted or unsubstituted Aryl group having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl group having 5 to 60 carbon atoms, substituted or unsubstituted heteroaryl group having 6 to 30 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, substituted Or an unsubstituted C1-C30 alkylamino group, a substituted or unsubstituted C6-C30 arylamino group, a substituted or unsubstituted C6-C30 aralkylamino group, a substituted or unsubstituted C2-C24 hetero It is selected from the group consisting of an arylamino group, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, and a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, Adjacent groups may combine with each other to form a substituted or unsubstituted ring.

The host is a fluorene-containing compound, a carbazole-containing compound, a dibenzofuran-containing compound, a dibenzothiophene-containing compound, an indenocarbazole-containing compound, an indolocarbazole-containing compound, a benzofurocarba sol-containing compounds, benzothienocarbazole-containing compounds, acridine-containing compounds, dihydroacridine-containing compounds, triindolobenzene-containing compounds, pyridine-containing compounds, pyrimidine-containing compounds, tri It may be selected from the group consisting of azine-containing compounds, silicon-containing compounds, cyano group-containing compounds, phosphine oxide-containing compounds, sulfoxide-containing compounds, sulfonyl-containing compounds and anthracene-containing compounds, but the above examples It is not limited to, and host materials that can be used in combination with the first dopant and the second dopant described above can be used without limitation.

Specifically, the host material may be one or more selected from the group consisting of the following compounds:

here,

n is an integer from 0 to 5;

R is hydrogen, heavy hydrogen, a cyano group, a nitro group, a halogen group, a hydroxyl group, a substituted or unsubstituted alkylthio group having 1 to 4 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, or a substituted or unsubstituted carbon atom 1 to 20 cycloalkyl groups, substituted or unsubstituted C2-30 alkenyl groups, substituted or unsubstituted C2-24 alkynyl groups, substituted or unsubstituted C7-30 aralkyl groups, substituted or unsubstituted Aryl group having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl group having 5 to 60 carbon atoms, substituted or unsubstituted heteroaryl group having 6 to 30 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, substituted Or an unsubstituted C1-C30 alkylamino group, a substituted or unsubstituted C6-C30 arylamino group, a substituted or unsubstituted C6-C30 aralkylamino group, a substituted or unsubstituted C2-C24 hetero It is selected from the group consisting of an arylamino group, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, and a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, Adjacent groups may combine with each other to form a substituted or unsubstituted ring.

Hereinafter, the organic electroluminescent device of the present invention will be described as an example. However, the content exemplified below does not limit the organic electroluminescent device of the present invention.

The organic light emitting device of the present invention may have a structure in which an anode (hole injection electrode), a hole injection layer (HIL), a hole transport layer (HTL), a light emitting layer (EML), and a cathode (electron injection electrode) are sequentially stacked, Preferably, an electron blocking layer (EBL) may be further included between the anode and the light emitting layer, and an electron transport layer (ETL) and an electron injection layer (EIL) may be further included between the cathode and the light emitting layer. In addition, a hole blocking layer (HBL) may be further included between the cathode and the light emitting layer.

In the manufacturing method of the organic light emitting device according to the present invention, first, an anode is formed by coating a substrate surface with a material for an anode in a conventional manner. At this time, the substrate used is preferably a glass substrate or a transparent plastic substrate having excellent transparency, surface smoothness, ease of handling, and water resistance. In addition, as the material for the anode, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO 2 ), zinc oxide (ZnO), etc., which are transparent and have excellent conductivity, may be used.

Next, a hole injection layer (HIL) material is vacuum thermally deposited or spin-coated on the surface of the anode in a conventional manner to form a hole injection layer. Materials for the hole injection layer include copper phthalocyanine (CuPc), 4,4',4"-tris(3-methylphenylamino)triphenylamine (m-MTDATA), and 4,4',4"-tris(3-methylphenyl). Amino) phenoxybenzene (m-MTDAPB), starburst amines 4,4',4"-tri(N-carbazolyl)triphenylamine (TCTA), 4,4',4"-tris (N-(2-naphthyl)-N-phenylamino)-triphenylamine (2-TNATA) or IDE406 available from Idemitsu is exemplified.

A hole transport layer (HTL) material is vacuum thermally deposited or spin-coated on the surface of the hole injection layer in a conventional manner to form a hole transport layer. At this time, the hole transport layer material is bis (N- (1-naphthyl-n-phenyl)) benzidine (α-NPD), N, N'-di (naphthalen-1-yl) -N, N'-biphenyl -benzidine (NPB) or N,N'-biphenyl-N,N'-bis(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine (TPD).

A light-emitting layer (EML) material is vacuum thermally deposited or spin-coated on the surface of the hole transport layer in a conventional manner to form the light-emitting layer. At this time, in the case of the light emitting layer material dopant and host material used, the compound of the present invention may be preferably used.

The dopant and host material in the emission layer may include 3 to 50 wt% of the first dopant, 0.5 to 5 wt% of the second fluorescent dopant, and the rest of the host material.

Optionally, an electron blocking layer (EBL) may be further formed between the hole transport layer and the light emitting layer.

An electron transport layer (ETL) material is vacuum thermally deposited or spin-coated on the surface of the light emitting layer in a conventional manner to form an electron transport layer. At this time, the electron transport layer material used is not particularly limited, and preferably tris(8-hydroxyquinolinolato) aluminum (Alq ₃ ) may be used.

Optionally, by additionally forming a hole blocking layer (HBL) between the light emitting layer and the electron transport layer and using a phosphorescent dopant in the light emitting layer together, diffusion of triplet excitons or holes into the electron transport layer can be prevented. .

Formation of the hole blocking layer may be carried out by vacuum thermal evaporation and spin coating of the hole blocking layer material in a conventional manner. In the case of the hole blocking layer material, it is not particularly limited, but preferably (8-hydroxyquinolinola To) lithium (Liq), bis(8-hydroxy-2-methylquinolinato)-aluminum biphenoxide (BAlq), bathocuproine (BCP), LiF, and the like can be used.

An electron injection layer (EIL) material is vacuum thermally deposited or spin-coated on the surface of the electron transport layer in a conventional manner to form an electron injection layer. In this case, materials such as LiF, Liq, Li ₂ O, BaO, NaCl, and CsF may be used as the material for the electron injection layer.

An anode is formed by vacuum thermally depositing a cathode material on the surface of the electron injection layer in a conventional manner.

At this time, the negative electrode material used is lithium (Li), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium (Mg), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag) and the like may be used. In addition, in the case of a top emission organic light emitting device, a transparent cathode through which light can pass may be formed using indium tin oxide (ITO) or indium zinc oxide (IZO).

A capping layer CPL may be formed on a surface of the negative electrode using a composition for forming a capping layer.

Hereinafter, methods for synthesizing the above compounds will be described below with representative examples. However, the method for synthesizing the compounds of the present invention is not limited to the methods exemplified below, and the compounds of the present invention may be prepared by methods exemplified below and methods known in the art.

[Synthesis Example 1: Preparation of Compound 1-411]

After putting the starting material A 1-411 in 200 mL of o-dichlorobenzene, 3.88 mL (40 mmol) of boron tribromide was added. Thereafter, the mixture was stirred at 180° C. for 24 hours. After cooling the reaction mixture to room temperature, 7.02mL (40mmol) of N,N-diisopropylethylamine was added thereto, followed by stirring at 60°C for 2 hours. After cooling to room temperature and slowly adding methanol, the mixture was stirred for 30 minutes. After obtaining the precipitated solid by filtration, it was recrystallized with dichloromethane and acetone to obtain 3.84 g of the compound 1-411 in 35% yield.

MS (MALDI-TOF) m/z: 1096 [M]+

[Synthesis Example 2: Preparation of Compound 1-1]

After dissolving 8.92g (20.0mmol) of starting material A 1-1 in 100ml of tert-butylbenzene, the mixture was cooled to 0 ^° C. 24.7 ml (42.0 mmol) of a 1.7M tert-butyllithium solution (in Pentane) was added under a nitrogen atmosphere, and the mixture was stirred at 60° C. for 2 hours. Thereafter, the reaction mixture was cooled to 0° C., and 4.00 ml (42.0 mmol) of boron tribromide was added thereto, followed by stirring at room temperature for 0.5 hour. The reactant was cooled to 0°C again, and after adding 7.3ml (42.0mmol) of N,N- diisopropylethylamine, the mixture was stirred at 60°C for 2 hours. The reaction solution was cooled to room temperature, and the organic layer was extracted using ethyl acetate and water. After removing the solvent of the extracted organic layer, it was purified using a silica gel column chromatography (DCM/Hexane) method. Thereafter, 1.77 g of the compound 1-1 was obtained in a yield of 21.0% by recrystallization and purification using a DCM/Acetone mixed solvent.

MS (MALDI-TOF) m/z: 420 [M]+

[Synthesis Example 3: Preparation of Compound 1-413]

Compound 1-413 was prepared in the same manner as in Synthesis Example 2, except that starting material A 1-413 was changed to 15.2 g (20.0 mmol). 4.14 g was obtained in 28.1% yield.

MS (MALDI-TOF) m/z: 734 [M]+

[Synthesis Example 4: Preparation of Compound 1-412]

29.7g (50.0mmol) of starting material A 1-412 was dissolved in 100ml of tert-butylbenzene and then cooled to 0 ^° C. 31.2ml (50.0mmol) of 1.6M n-butyllithium solution (in Hexane) was added under a nitrogen atmosphere, and after stirring at 70°C for 4 hours, hexane was removed again at 100°C. Thereafter, the reactant was cooled to -40°C, 5.78ml (60.0mmol) of boron tribromide was added, and the mixture was stirred at room temperature for 1 hour and then stirred again at 40°C for 1 hour. The reactant was cooled to 0°C again, and 19.3ml (150.0mmol) of N,N-diisopropylethylamine was added thereto, followed by stirring at 120°C for 12 hours. The reaction solution was cooled to room temperature, and the organic layer was extracted using ethyl acetate and water. After removing the solvent of the extracted organic layer, it was purified using a silica gel column chromatography (DCM/Hexane) method. After recrystallization and purification with methanol solvent, 13.8 g of the compound 1-412 was obtained in a yield of 45.7%.

MS (MALDI-TOF) m/z: 603 [M]+

[Synthesis Example 5: Preparation of Compound 1-414]

4.61 g (10.0 mmol) of starting materials A 1-414 and B 1-414 and 1.92 g (20.0 mmol) of sodium-tert butoxide were added, dissolved in 100 ml of toluene, and tri-tert-butylphosphine/tetrafluoro After adding 0.23 g (0.8 mmol) of borate and stirring at 80 ° C for 15 minutes in a nitrogen atmosphere, after adding 0.18 g (0.2 mmol) of tris (dibenzylidene acetone) dipalladium (0), it was refluxed at 120 ° C for 18 hours. did After completion of the reaction, after cooling to room temperature, the organic layer was extracted using 300 ml of water and 300 ml of dichloromethane, dried with MgSO4, distilled off the filtrate, purified by column chromatography, and recrystallized with hexane/dichloromethane to obtain the compound 1-414 4.22 g was obtained in 48.0% yield.

MS (MALDI-TOF) m/z: 877 [M]+

[Synthesis Example 6: Preparation of Compound 1-415]

Compound 1-415 was prepared in the same manner as in Synthesis Example 5, except that the starting material B 1-414 was changed to 2.30 g (11.0 mmol) of B 1-415. 2.93 g was obtained in 49.6% yield.

MS (MALDI-TOF) m/z: 589 [M]+

[Synthesis Example 7: Preparation of Compound 2-83]

4.40 g of the compound 2-83 was obtained in a yield of 37.3% in the same manner as in Synthesis Example 1, except that the starting material A 1-411 was changed to 11.6 g (10 mmol) of A 2-83.

MS (MALDI-TOF) m/z: 1176 [M]+

[Synthesis Example 8: Preparation of Compound 2-84]

starting material A 1-411 4.21 g of the compound 2-84 was obtained in a yield of 33.3% using the same method as in Synthesis Example 1, except that 12.4 g (10 mmol) of A 2-84 was used.

MS (MALDI-TOF) m/z: 1261 [M]+

[Synthesis Example 9: Preparation of Compound 2-85]

starting material A 1-411 A 2-85 3.88 g of the compound 2-85 was obtained in a yield of 34.1% using the same method as in Synthesis Example 1, except that the amount was changed to 11.2 g (10 mmol).

MS (MALDI-TOF) m/z: 1137 [M]+

[Synthesis Example 10: Preparation of Compound 2-86]

Starting materials A 2-86 and B 2-86 16.0 g (50.0 mmol) and tris (dibenzylideneacetone) dipalladium (0) 0.18 g (0.2 mmol) and 2-dicyclohexylphosphino-2', 6' - Add 0.32 g (0.8 mmol) of dimethoxybiphenyl to 150 ml of toluene, and heat to 100°C in a nitrogen atmosphere. Thereafter, 50ml (50.0mmol) of 1M lithium bis(trimethylsilyl)amide THF solution was added and refluxed at 110°C for 10 hours. After completion of the reaction, the reactant was filtered with celite, the organic layer was extracted using 200 ml of water and 300 ml of dichloromethane, dried with MgSO4, the filtrate was distilled, purified by column chromatography, and recrystallized with hexane/dichloromethane to obtain the above compound 2-86 3.81 g was obtained in 43.2% yield.

MS (MALDI-TOF) m/z: 879 [M]+

[Synthesis Example 11: Preparation of Compound 2-87]

Compound 2-87 was prepared in the same manner as in Synthesis Example 10, except that the starting material B 2-86 was changed to 18.87 g (50.0 mmol) of B 2-87. 3.88 g was obtained in 39.1% yield.

MS (MALDI-TOF) m/z: 991 [M]+

[Synthesis Example 12: Preparation of Compound 2-88]

Starting material A 2-88 was added to 150 ml of N, N-dimethylformamide, and tetrabutylammonium hydroxide (37% methanol solution) 15.5ml (22.0mmol) and copper iodide (Ⅰ) 1.91g (10.0 ml) mmol) was added, and the mixture was refluxed at 120° C. for 24 hours in a nitrogen atmosphere. After completion of the reaction, the reaction solution was filtered, and the obtained solid was Soxhlet purified with chlorobenzene and filtered to obtain the compound 2-88 1.32 g was obtained in 21.5% yield.

MS (MALDI-TOF) m/z: 612 [M]+

[Synthesis Example 13: Preparation of Compound 2-89]

Starting materials A 2-89 3.60g (10.0mmol) and B 2-89 3.38g (20.0mmol), tris(dibenzylideneacetone)dipalladium(0) 0.36g (0.4mmol), tris-tert-butylphosphine After putting 0.16g (0.8mmol) and 3.84g (40.0mmol) of sodium tert-butoxide in a flask, the mixture was stirred at 90 ^° C. for 6 hours in a nitrogen atmosphere with 100ml of toluene. After confirming the completion of the reaction by TLC (Thin Layer Chromatography), the organic layer was extracted using toluene and water. The extracted solution was mixed with MgSO ₄ It was treated to remove residual moisture and dried in a vacuum oven. Thereafter, 2.99 g of compound 2-89 was obtained in a yield of 55.7% by column chromatography (dichloromethane, heptane).

MS (MALDI-TOF) m/z: 536 [M]+

[Synthesis Example 14: Preparation of Compound 2-90]

3.54 g of the compound 2-90 was obtained in a yield of 46.5% using the same method as in Synthesis Example 13, except that the starting material B 2-89 was changed to 5.62 g (20 mmol) of B 2-90.

MS (MALDI-TOF) m/z: 760 [M]+

[Synthesis Example 15: Preparation of Compound 2-91]

starting material A 2-89 4.16 g of the compound 2-91 was prepared in the same manner as in Synthesis Example 13, except that A 2-91 4.48 g (10 mmol) and B 2-89 were changed to B 2-91 6.68 g (20 mmol). It was obtained in 59.2% yield.

MS (MALDI-TOF) m/z: 701 [M]+

[Synthesis Example 16: Synthesis of Compound 2-92]

Starting materials A 2-92 5.64g (10.0mmol) and B 2-89 3.38g (20.0mmol), tris(dibenzylideneacetone)dipalladium(0) 0.36g (0.4mmol), tris-tert-butylphosphine After putting 0.16g (0.8mmol) and 3.84g (40.0mmol) of sodium tert-butoxide in a flask, the mixture was stirred at 90 ^° C. for 6 hours in a nitrogen atmosphere with 100ml of toluene. After confirming the completion of the reaction by TLC (Thin Layer Chromatography), the organic layer was extracted using toluene and water. The extracted solution was mixed with MgSO ₄ It was treated to remove residual moisture and dried in a vacuum oven. Thereafter, 3.68 g of compound 2-92 was obtained in a yield of 49.6% by column chromatography (dichloromethane, heptane).

MS (MALDI-TOF) m/z: 740 [M]+

[Synthesis Example 17: Preparation of Compound 2-93]

The same method as in Synthesis Example 16 was used except that the starting material A 2-92 was changed to 5.80 g (10 mmol) of A 2-93 and 5.38 g (20 mmol) of B 2-89 B 2-93. 4.89 g of compound 2-93 was obtained in a yield of 51.0%.

MS (MALDI-TOF) m/z: 956 [M]+

[Synthesis Example 18: Preparation of Compound 2-94]

Using the same method as in Synthesis Example 16, except that the starting material A 2-92 was changed to A 2-94 5.66 g (10 mmol) and B 2-89 B 2-94 5.70 g (20 mmol) 5.14 g of compound 2-94 was obtained in a yield of 52.7%.

MS (MALDI-TOF) m/z: 974 [M]+

[Synthesis Example 19: Preparation of Compound 3-16]

Starting materials A 3-16 5.56 g (10.0 mmol) and B 3-16 2.85 g (10.0 mmol) and potassium carbonate 2.76 g (20.0 mmol) and tetrakis (triphenylphosphine) palladium (0) 0.23 g (0.2 mmol) ) was added, dissolved in 100 ml of toluene, 20 ml of water, and 20 ml of ethanol, stirred for 30 minutes in a nitrogen atmosphere, and then refluxed at 80° C. for 12 hours. After completion of the reaction, after cooling to room temperature, the organic layer was extracted using 200 ml of water and 300 ml of dichloromethane, dried with MgSO4, distilled off the filtrate, purified by column chromatography, and recrystallized with hexane/dichloromethane to obtain the compound 3-16 3.91 g was obtained in 61.5% yield.

MS (MALDI-TOF) m/z: 634 [M]+

[Synthesis Example 20: Preparation of Compound 3-42]

Using the same method as in Synthesis Example 19, except that the starting material A 3-16 was changed to B 3-42 7.14 g (20 mmol) and B 3-16 was changed to A 3-42 3.14 g (10 mmol). 3.22 g of compound 3-42 was obtained in a yield of 52.2%.

MS (MALDI-TOF) m/z: 615 [M]+

[Synthesis Example 21: Preparation of Compound 3-43]

starting material A 3-16 2.84 g of the compound 3-43 was obtained in 48.4% yield using the same method as in Synthesis Example 19, except that B 3-43 and B 3-16 were changed to 5.92 g (10 mmol) of A 3-43. .

MS (MALDI-TOF) m/z: 586 [M]+

[Synthesis Example 22: Preparation of Compound 3-39]

3.95 g (10.0 mmol) of starting material A 3-39 and 4.37 g (9.0 mmol) of B 3-39 and 1.92 (20.0 mmol) of sodium tert-butoxide were added, dissolved in 100 ml of toluene, and stirred for 30 minutes in a nitrogen atmosphere. Then, 0.08 g (0.4 mmol) of tri-tert-butylphosphine and 0.18 g (0.2 mmol) of tris (dibenzylideneacetone) dipalladium (0) were added, and the mixture was refluxed at 100° C. for 12 hours. After completion of the reaction, after cooling to room temperature, the organic layer was extracted using 200 ml of water and 300 ml of dichloromethane, dried with MgSO4, distilled off the filtrate, purified by column chromatography, and recrystallized with hexane/dichloromethane to obtain the compound 3-39 5.62 g was obtained in 70.1% yield.

MS (MALDI-TOF) m/z: 800 [M]+

[Synthesis Example 23: Preparation of Compound 3-40]

starting material A 3-39 7.34 g of the compound 3-40 was prepared in the same manner as in Synthesis Example 16, except that 3.12 g (10 mmol) of A 3-40 and B 3-39 were changed to 8.21 g (10 mmol) of B 3-40. It was obtained in 75.5% yield.

MS (MALDI-TOF) m/z: 970 [M]+

[Synthesis Example 24: Preparation of Compound 3-41]

starting material A 3-39 5.47 g of the compound 3-41 was obtained in 76.0% yield using the same method as in Synthesis Example 16, except that B 3-39 was changed to 4.01 g (10 mmol) of B 3-41 as A 3-41. .

MS (MALDI-TOF) m/z: 718 [M]+

[Synthesis Example 25: Preparation of Compound 3-17]

After putting 10.03 g (60.0 mmol) of starting materials A 3-17 and B 3-17 in 100 ml of o-dichlorobenzene, 7.62 g (120.0 mmol) of copper, 33.17 g (240.0 mmol) of potassium carbonate, 18-crown -6 4.32g (12.0mmol) was added and stirred at 190oC for 36 hours. After completion of the reaction, the solvent was removed by distillation under reduced pressure, and the organic layer was separated using water and chloroform. After removing water using MgSO4, the organic layer was filtered and distilled under reduced pressure to remove the solvent. The resulting solid was subjected to silica gel column chromatography (DCM/Hexane) to obtain 5.01 g of Compound 3-17 in a yield of 61.3%.

MS (MALDI-TOF) m/z: 408 [M]+

[Synthesis Example 26: Synthesis of Compound 3-18]

starting material A 3-17 4.63 g of the compound 3-18 was obtained in a yield of 47.7% using the same method as in Synthesis Example 25, except that 6.24 g (20 mmol) of A 3-18 was used.

MS (MALDI-TOF) m/z: 484 [M]+

[Synthesis Example 27: Preparation of Compound 3-19]

5.17 g of the compound 3-19 was obtained in a yield of 53.3% using the same method as in Synthesis Example 25, except that the starting material A 3-17 was changed to 6.24 g (20 mmol) of A 3-19.

MS (MALDI-TOF) m/z: 484 [M]+

[Example]

Manufacture of organic electroluminescent device

The organic electroluminescent devices of Examples 1 to 84 were manufactured in the following manner. The substrate on which Ag, the light-reflection layer, and ITO (10 nm), the anode of the organic electroluminescent device were sequentially stacked, were divided into cathode and anode regions and an insulating layer through a photo-lithograph process, and then patterned. For the purpose of cleaning and increasing the work-function of the anode (ITO), the surface was treated with O ₂ :N ₂ plasma. 1,4,5,8,9,11-hexaazatriphenylene-hexacarbonitrile (HAT-CN) was formed thereon to a thickness of 100 Å as a hole injection layer (HIL).

Next, on the hole injection layer, N4, N4, N4', N4'-tetra ([1,1'-biphenyl] -4-yl) - [1,1'-biphenyl] -4,4'- A hole transport layer having a thickness of 1000 Å was formed by vacuum deposition of diamine. As an electron blocking layer (EBL) on the hole transport layer (HTL), N-phenyl-N-(4-(spiro[benzo[de]anthracene-7,9'-fluorene]-2'-yl)phenyl)di Benzo[b,d]furan-4-amine is formed to a thickness of 100 Å, and the first host and the second host are used alone or deposited in a 5:5 ratio as a host of the light emitting layer on the electron blocking layer (EBL). At the same time, 20 wt% of the first dopant and 1 wt% of the second dopant were doped as dopants to form a light emitting layer (EML) with a thickness of 200 Å.

2-(4-(9,10-di(naphthalen-2-yl)anthracen-2-yl)phenyl)-1-phenyl-1H-benzo[d]imidazole and Liq were added together in a 1:1 ratio on the top of the light emitting layer. Deposited to form an electron transport layer (ETL) with a thickness of 360 Å, Yb was deposited with a thickness of 10 Å as an electron injection layer, and magnesium (Mg) and silver (Ag) were deposited with a thickness of 130 Å at a ratio of 1:9 as a cathode.

As a capping layer on the cathode, N4,N4'-diphenyl-N4,N4'-bis(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-[1,1'-biphenyl]- 4,4'-diamine was deposited to a thickness of 650 Å. An organic EL device was manufactured by attaching a seal cap with a UV curable adhesive on the capping layer (CPL) to protect the organic EL device from O ₂ or moisture in the air.

Combinations of host and dopant materials used in Examples and Comparative Examples are shown in Table 1 below. The following structures were introduced into the organic electroluminescent devices of Examples 1 to 84 as first dopant and second dopant materials of Synthesis Example:

The following structures were introduced into the organic electroluminescent devices of Comparative Examples 1 to 16 as first dopant and second dopant structures of Comparative Examples:

[Comparative Example]

Element creation example 1st host 2nd host first dopant Second dopant Example 1 compounds 3-17 - compound 1-411 compound 2-83 Example 2 - compound 1-1 compound 2-84 Example 3 - compound 1-412 compound 2-86 Example 4 - compound 1-412 compound 2-89 Example 5 - compound 1-412 compound 2-92 Example 6 - compound 1-413 compound 2-86 Example 7 - compound 1-414 compound 2-89 Example 8 - compound 1-414 compound 2-92 Example 9 - compound 1-415 compound 2-89 Example 10 - compound 1-415 compound 2-92 Example 11 compounds 3-18 - compound 1-411 compound 2-83 Example 12 - compound 1-1 compound 2-84 Example 13 - compound 1-412 compound 2-86 Example 14 - compound 1-412 compound 2-89 Example 15 - compound 1-412 compound 2-92 Example 16 - compound 1-413 compound 2-86 Example 17 - compound 1-414 compound 2-89 Example 18 - compound 1-414 compound 2-92 Example 19 - compound 1-415 compound 2-89 Example 20 - compound 1-415 compound 2-92 Example 21



compounds 3-19 - compound 1-411 compound 2-83 Example 22 - compound 1-1 compound 2-84 Example 23 - compound 1-412 compound 2-86 Example 24 - compound 1-412 compound 2-89 Example 25 - compound 1-412 compound 2-92 Example 26 - compound 1-413 compound 2-86 Example 27 - compound 1-414 compound 2-89 Example 28 - compound 1-414 compound 2-92 Example 29 - compound 1-415 compound 2-89 Example 30 - compound 1-415 compound 2-92 Example 31 compounds 3-39 Compounds 3-16 compound 1-412 compound 1-411 Example 32 compound 1-412 compound 2-93 Example 33 compound 1-414 compound 2-91 Example 34 compound 1-414 compound 2-86 Example 35 compound 1-415 compound 2-93 Example 36 compound 1-415 compound 2-91 Example 37 Compounds 3-40 Compounds 3-16 compound 1-412 compound 2-87 Example 38 compound 1-412 compound 2-94 Example 39 compound 1-414 compound 2-83 Example 40 compound 1-414 compound 2-87 Example 41 compound 1-414 compound 2-94 Example 42 compound 1-415 compound 2-89 Example 43 compound 3-41 Compounds 3-16 compound 1-412 compound 2-88 Example 44 compound 1-412 compound 2-92 Example 45 compound 1-414 compound 2-90 Example 46 compound 1-414 compound 2-88 Example 47 compound 1-415 compound 2-84 Example 48 compound 1-415 compound 2-90 Example 49 compounds 3-39 compound 3-42 compound 1-412 compound 2-86 Example 50 compound 1-412 compound 2-85 Example 51 compound 1-414 compound 2-91 Example 52 compound 1-414 compound 2-86 Example 53 compound 1-415 compound 2-93 Example 54 compound 1-415 compound 2-91 Example 55 Compounds 3-40 compound 3-42 compound 1-412 compound 2-87 Example 56 compound 1-412 compound 2-94 Example 57 compound 1-414 compound 2-89 Example 58 compound 1-414 compound 1-411 Example 59 compound 1-414 compound 2-94 Example 60 compound 1-415 compound 2-89 Example 61 compound 3-41 compound 3-42 compound 1-412 compound 2-88 Example 62 compound 1-412 compound 2-92 Example 63 compound 1-414 compound 2-90 Example 64 compound 1-414 compound 2-88 Example 65 compound 1-415 compound 2-92 Example 66 compound 1-415 compound 2-83 Example 67 compounds 3-39 compound 3-43 compound 1-412 compound 2-84 Example 68 compound 1-412 compound 2-93 Example 69 compound 1-414 compound 2-91 Example 70 compound 1-414 compound 2-86 Example 71 compound 1-415 compound 2-93 Example 72 compound 1-415 compound 2-91 Example 73 Compounds 3-40 compound 3-43 compound 1-412 compound 2-87 Example 74 compound 1-412 compound 2-94 Example 75 compound 1-414 compound 2-85 Example 76 compound 1-414 compound 2-87 Example 77 compound 1-415 compound 1-411 Example 78 compound 1-415 compound 2-89 Example 79 compound 3-41 compound 3-43 compound 1-412 compound 2-88 Example 80 compound 1-412 compound 2-83 Example 81 compound 1-414 compound 2-90 Example 82 compound 1-414 compound 2-88 Example 83 compound 1-415 compound 2-92 Example 84 compound 1-415 compound 2-90 Comparative Example 1 compounds 3-17 - D-1A - Comparative Example 2 compounds 3-17 - D-2A - Comparative Example 3 compounds 3-18

- D-3A - Comparative Example 4 compounds 3-18 - D-4A - Comparative Example 5 compounds 3-39 Compounds 3-16 D-1A - Comparative Example 6 Compounds 3-40 compound 3-42 D-2A
- Comparative Example 7 compound 3-41 compound 3-43 D-3A - Comparative Example 8 Compounds 3-40 Compounds 3-16 D-4A - Comparative Example 9 compounds 3-17 - D-1A compound 2-86 Comparative Example 10 compounds 3-17 - D-2A compound 2-89 Comparative Example 11 compounds 3-18 - D-3A compound 2-90 Comparative Example 12 compounds 3-18 - D-4A compound 2-92 Comparative Example 13 compounds 3-39 Compounds 3-16 D-1A compound 2-86 Comparative Example 14 Compounds 3-40 compound 3-42 D-2A compound 2-89 Comparative Example 15 compound 3-41 compound 3-43 D-3A compound 2-90 Comparative Example 16 Compounds 3-40 Compounds 3-16 D-4A compound 2-92

[Experimental Example: Measurement of Light Emission Characteristics of Organic Light-Emitting Diode]

In order to evaluate the characteristics of the organic electroluminescent device according to Examples and Comparative Examples, lifetime and device efficiency were measured. The device efficiency is a value for a current density of 10 mA/cm 2 . Table 2 shows the lifespan results of the lifespan time (T95) falling from 100% to 90% at a constant current based on 1,000 nit luminance. Evaluation results in Table 2 show Example compounds 3-16, 3-42, 3-43, 3-39, 3-40, 3-41, 3-17, 3-18, 3-19 as the first and second hosts , and Example Compounds 1-411, 1-1, 1-412, 1-413, 1-414, and 1-415 were used as the first dopant, and Example Compounds 1-411, 2-83, and 2 -84, 2-85, 1-1, 1-412, 1-413, 2-86, 2-87, 2-88, 2-89, 2-90, 2-91, 2-92, 2-93 , 2-94 was used as the second dopant.

Element creation example Voltage (V) EQE (%) Lifetime (hr)
(T90, @1000nit) Example 1 4.19 12.1 41.5 Example 2 4.18 12.3 52 Example 3 4.36 10.8 50.5 Example 4 4.37 10.6 51 Example 5 4.31 11.1 49 Example 6 4.38 10.4 42 Example 7 4.30 11.3 51 Example 8 4.32 11.1 50 Example 9 4.36 10.7 68 Example 10 4.38 10.5 50.5 Example 11 4.20 12.4 43 Example 12 4.19 12.2 52.5 Example 13 4.35 10.9 51 Example 14 4.38 10.4 48 Example 15 4.31 11.3 49.5 Example 16 4.36 10.5 42.5 Example 17 4.29 11.4 51 Example 18 4.30 11.4 50.5 Example 19 4.36 10.5 48 Example 20 4.28 11.6 52 Example 21 4.18 12.5 39 Example 22 4.19 12.1 52 Example 23 4.29 11.7 50.5 Example 24 4.38 10.6 49 Example 25 4.37 10.5 48.5 Example 26 4.39 10.2 36. Example 27 4.32 11.2 50.5 Example 28 4.31 11.4 51 Example 29 4.37 10.9 47.5 Example 30 4.22 11.8 51 Example 31 4.20 12.4 62 Example 32 4.19 12.5 68.5 Example 33 4.22 11.7 65 Example 34 4.29 10.5 71 Example 35 4.19 12.3 67 Example 36 4.20 12.1 64.5 Example 37 4.24 11.1 61.5 Example 38 4.24 11.2 72 Example 39 4.21 11.9 68 Example 40 4.17 12.9 71.5 Example 41 4.22 11.6 69 Example 42 4.18 12.6 65 Example 43 4.28 10.8 63 Example 44 4.21 11.7 68.5 Example 45 4.25 11.3 60.5 Example 46 4.19 12.5 69 Example 47 4.20 12.4 67 Example 48 4.16 12.7 62 Example 49 4.10 13.3 64.5 Example 50 4.15 12.8 72 Example 51 4.19 12.1 65 Example 52 4.23 11.7 59 Example 53 4.13 12.2 68 Example 54 4.12 12.7 64.5 Example 55 4.22 11.7 61.5 Example 56 4.19 12.1 70.5 Example 57 4.09 13.2 65 Example 58 4.21 11.9 62 Example 59 4.17 12.3 59.5 Example 60 4.08 13.5 62 Example 61 4.16 12.4 51.5 Example 62 4.11 12.9 68 Example 63 4.10 12.9 70 Example 64 4.09 13.1 66.5 Example 65 4.15 12.7 64 Example 66 4.11 13.2 59.5 Example 67 4.18 12.5 60 Example 68 4.19 12.6 65 Example 69 4.23 11.8 70.5 Example 70 4.22 11.9 64 Example 71 4.16 12.4 53.5 Example 72 4.21 11.5 68 Example 73 4.23 11.4 64 Example 74 4.23 11.3 61.5 Example 75 4.29 10.8 61 Example 76 4.12 13.2 61.5 Example 77 4.22 11.6 64.5 Example 78 4.21 11.6 50.5 Example 79 4.19 11.8 63.5 Example 80 4.17 12.7 63 Example 81 4.24 11.1 67 Example 82 4.13 12.5 59 Example 83 4.20 11.4 72 Example 84 4.14 12.9 65.5 Comparative Example 1 4.33 7.2 2 Comparative Example 2 4.36 6.9 2.5 Comparative Example 3 4.36 6.7 2 Comparative Example 4 4.32 7.1 1.5 Comparative Example 5 4.31 7.5 1.5 Comparative Example 6 4.32 7.3 2 Comparative Example 7 4.34 7.0 2.5 Comparative Example 8 4.35 7.2 One Comparative Example 9 4.30 8.6 10.5 Comparative Example 10 4.32 8.3 12 Comparative Example 11 4.33 8.0 11.5 Comparative Example 12 4.31 8.4 10 Comparative Example 13 4.27 9.9 18 Comparative Example 14 4.26 9.6 22.5 Comparative Example 15 4.26 9.3 19.5 Comparative Example 16 4.27 9.8 18.5

According to the above experimental results, compared to Comparative Examples 1 to 16, when the compounds of Examples of the present invention are used, an organic light emitting device having excellent characteristics such as efficiency and lifespan can be provided.

Although the preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements of those skilled in the art using the basic concept of the present invention defined in the following claims are also made according to the present invention. falls within the scope of the rights of

Claims (8)

A first electrode, a second electrode opposite the first electrode, and an organic layer disposed between the first electrode and the second electrode,
The organic layer includes a light emitting layer,
The light emitting layer includes a host, a first dopant and a second dopant,
The first dopant exhibits delayed fluorescence characteristics, and the second dopant exhibits fluorescence characteristics,
The first dopant is an organic electroluminescent device including a compound represented by Formula 1 or a multimer compound including a compound represented by Formula 1 as a unit structure:
[Formula 1]

here,
Ring A, ring B and ring C are the same as or different from each other, and each independently represents a substituted or unsubstituted aryl group having 5 to 30 carbon atoms or a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms,
Z is B or N;
X ₁ and Y ₁ are the same as or different from each other, and are each independently selected from the group consisting of N(R ₁ ), C(R ₂ )(R ₃ ), O and S,
At least one or more X ₁ and Y ₁ are bonded to adjacent A-rings to C-rings to form a ring compound;
R ₁ to R ₃ are the same as or different from each other, and each independently represents hydrogen, heavy hydrogen, a cyano group, a nitro group, a halogen group, a hydroxy group, a substituted or unsubstituted alkylthio group having 1 to 4 carbon atoms, or a substituted or unsubstituted carbon number. Alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted cycloalkyl group having 1 to 20 carbon atoms, substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, substituted or unsubstituted alkynyl group having 2 to 24 carbon atoms, substituted or unsubstituted Aralkyl group having 7 to 30 carbon atoms, substituted or unsubstituted aryl group having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl group having 5 to 60 carbon atoms, substituted or unsubstituted heteroarylalkyl group having 6 to 30 carbon atoms, substituted Or an unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, or a substituted or unsubstituted aralkyl group having 6 to 30 carbon atoms Amino group, substituted or unsubstituted heteroarylamino group having 2 to 24 carbon atoms, substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms and substituted or unsubstituted carbon atoms It is selected from the group consisting of 6 to 30 aryloxy groups, and may combine with adjacent groups to form a substituted or unsubstituted ring. According to claim 1,
The compound represented by Formula 1 is an organic electroluminescent device that is a compound represented by Formula 2 below:
[Formula 2]

here,
A, B, Z, X ₁ and Y ₁ are as defined in claim 1 above,
R ₄ to R ₆ are the same as or different from each other, and each independently represents hydrogen, heavy hydrogen, a cyano group, a nitro group, a halogen group, a hydroxy group, a substituted or unsubstituted alkylthio group having 1 to 4 carbon atoms, or a substituted or unsubstituted carbon number. Alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted cycloalkyl group having 1 to 20 carbon atoms, substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, substituted or unsubstituted alkynyl group having 2 to 24 carbon atoms, substituted or unsubstituted Aralkyl group having 7 to 30 carbon atoms, substituted or unsubstituted aryl group having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl group having 5 to 60 carbon atoms, substituted or unsubstituted heteroarylalkyl group having 6 to 30 carbon atoms, substituted Or an unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, or a substituted or unsubstituted aralkyl group having 6 to 30 carbon atoms Amino group, substituted or unsubstituted heteroarylamino group having 2 to 24 carbon atoms, substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms and substituted or unsubstituted carbon atoms It is selected from the group consisting of 6 to 30 aryloxy groups, and may combine with adjacent groups to form a substituted or unsubstituted ring. According to claim 1,
The A ring and the B ring are compounds selected from the group consisting of ring compounds represented by Formulas 3 to 8:
[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

here,

means the condensed part,
n, p, r and t are the same as or different from each other, and each independently represents an integer from 0 to 2,
m, q, s, and u are the same as or different from each other, and each independently represents an integer from 0 to 4;
X ₂ to X ₅ are the same as or different from each other, and are each independently selected from the group consisting of C (R ₁₅ ), N, and Si (R ₁₆ );
X ₆ to X ₁₀ are the same as or different from each other, and are each independently selected from the group consisting of C(R ₁₇ )(R ₁₈ ), N(R ₁₉ ), O, S, and Si(R ₂₀ )(R ₂₁ ); ,
R ₇ to R ₂₁ are the same as or different from each other, and each independently represents hydrogen, heavy hydrogen, a cyano group, a nitro group, a halogen group, a hydroxy group, a substituted or unsubstituted alkylthio group having 1 to 4 carbon atoms, or a substituted or unsubstituted carbon number. Alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted cycloalkyl group having 1 to 20 carbon atoms, substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, substituted or unsubstituted alkynyl group having 2 to 24 carbon atoms, substituted or unsubstituted Aralkyl group having 7 to 30 carbon atoms, substituted or unsubstituted aryl group having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl group having 5 to 60 carbon atoms, substituted or unsubstituted heteroarylalkyl group having 6 to 30 carbon atoms, substituted Or an unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, or a substituted or unsubstituted aralkyl group having 6 to 30 carbon atoms Amino group, substituted or unsubstituted heteroarylamino group having 2 to 24 carbon atoms, substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms and substituted or unsubstituted carbon atoms It is selected from the group consisting of 6 to 30 aryloxy groups, and may combine with adjacent groups to form a substituted or unsubstituted ring. delete delete According to claim 1,
The first dopant is included in an organic electroluminescent device in a greater amount than the second dopant in the organic layer. According to claim 1,
The second dopant is an organic electroluminescent device selected from the group consisting of a condensed ring-containing compound, an amino group-containing compound, a styryl group-containing compound, and a boron-containing compound. According to claim 1,
The host is a fluorene-containing compound, a carbazole-containing compound, a dibenzofuran-containing compound, a dibenzothiophene-containing compound, an indenocarbazole-containing compound, an indolocarbazole-containing compound, a benzofurocarba sol-containing compounds, benzothienocarbazole-containing compounds, acridine-containing compounds, dihydroacridine-containing compounds, triindolobenzene-containing compounds, pyridine-containing compounds, pyrimidine-containing compounds, tri An organic electroluminescent device selected from the group consisting of azine-containing compounds, silicon-containing compounds, cyano group-containing compounds, phosphine oxide-containing compounds, sulfoxide-containing compounds, sulfonyl-containing compounds and anthracene-containing compounds.