KR102626972B1 - Novel organic electroluminescence compounds and organic electroluminescence device comprising the same - Google Patents

Abstract

The present invention relates to a novel organic electroluminescent compound and an organic electroluminescent device containing the same. The organic electroluminescent compound according to the present invention has higher luminous efficiency than the conventional organic electroluminescent compound, and the compound of the present invention is used as an organic EL device. When used in the light-emitting layer of a device, the charge balance between holes and electrons in the light-emitting layer is well achieved, the current/power efficiency of the device is increased, and the driving voltage is lowered, thereby prolonging the lifespan.

Description

Novel organic electroluminescent compound and organic electroluminescent device comprising the same

The present invention relates to novel organic electroluminescent compounds and organic electroluminescent devices containing the same.

An electroluminescence device (EL device) is a self-luminous display device that has the advantages of a wide viewing angle, excellent contrast, and fast response speed. In 1987, Eastman Kodak developed the first organic EL device using low-molecular-weight aromatic diamine and aluminum complexes as materials for forming the light-emitting layer [Reference: Appl. Phys. Lett. 51, 913, 1987].

An organic electroluminescence device is a device that converts electrical energy into light by applying electricity to an organic light-emitting material, and usually has a structure including an anode (anode) and a cathode, and an organic material layer between them. The organic material layer of an organic electroluminescent device may be composed of a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer (including host and dopant materials), an electron buffer layer, a hole blocking layer, an electron transport layer, an electron injection layer, etc. Materials used are divided into hole injection materials, hole transport materials, electron blocking materials, light-emitting materials, electron buffer materials, hole blocking materials, electron transport materials, and electron injection materials depending on their functions. In such an organic electroluminescent device, holes are injected from the anode and electrons from the cathode are injected into the light-emitting layer by applying voltage, and excitons with high energy are formed by recombination of the holes and electrons. This energy causes the light-emitting organic compound to be excited, and as the excited state of the light-emitting organic compound returns to the ground state, the energy is emitted as light and emits light.

The light-emitting material of an organic electroluminescent device is the most important factor in determining the light-emitting efficiency of the device. The light-emitting material must have high quantum efficiency and high mobility of electrons and holes, and the formed light-emitting material layer must be uniform and stable. These light-emitting materials are divided into blue, green, or red light-emitting materials depending on the color of the light, and there are also yellow or orange light-emitting materials. Additionally, light-emitting materials can be divided into host materials and dopant materials from a functional standpoint. Recently, the development of organic electroluminescent devices with high efficiency and long lifespan has emerged as an urgent task. In particular, considering the level of EL characteristics required for medium to large-sized OLED panels, the development of materials that are significantly superior to existing light emitting materials is urgently needed. . For this purpose, the desirable characteristics of the host material, which acts as a solvent and energy carrier in the solid state, must be high purity and have an appropriate molecular weight to enable vacuum deposition. In addition, thermal stability must be secured due to the high glass transition temperature and thermal decomposition temperature, high electrochemical stability is required for long life, and it must be easy to form an amorphous thin film. It must have good adhesion to materials of other adjacent layers, but interlayer movement is difficult. You shouldn't.

To date, the iridium(III) complex series is widely known as a phosphorescent material, and (acac)Ir(btp) ₂ (bis(2-(2'-benzothienyl)-pyridinium) for each red, green, and blue emission. Naito-N,C3')iridium(acetylacetonate)), Ir(ppy) ₃ (tris(2-phenylpyridine)iridium) and Firpic(bis(4,6-difluorophenylpyridinato-N) Materials such as , C2) picolinate iridium) are known.

Light-emitting materials can be used by mixing hosts and dopants to improve color purity, luminous efficiency, and stability. When using such a dopant/host material system, the selection of the host material is important because it has a significant impact on the efficiency and performance of the light emitting device. In the prior art, 4,4'-N,N'-dicarbazole-biphenyl (CBP) was the most widely known phosphorescent host material. Recently, Bathocuproine (BCP) and aluminum(III) bis(2-methyl-8-quinolinate)(4-phenylphenolate), which were used as hole blocking layer materials by Pioneer and others in Japan. A high-performance organic EL device has been developed using Balq as a host material.

However, although these existing phosphorescent host materials are advantageous in terms of luminescent properties, they have the following disadvantages: (1) their glass transition temperature is low and thermal stability is low, so the material changes when subjected to a high-temperature deposition process under vacuum; . (2) In organic EL devices, power efficiency = [(π/voltage) × current efficiency], so power efficiency is inversely proportional to voltage. Organic EL devices using phosphorescent host materials have higher current efficiency (cd/A) than organic EL devices using fluorescent host materials, but the driving voltage is also quite high, so there is no significant advantage in terms of power efficiency (lm/W). (3) When used in organic EL devices, the operating life is also unsatisfactory, and luminous efficiency still requires improvement.

Therefore, in order to realize the excellent characteristics of an organic EL device, the materials constituting the organic layer within the device, especially the host or dopant constituting the light emitting material, must be appropriately selected. Meanwhile, Korean Patent Publication Nos. 10-2013-0139916 and 10-2013-0093460 describe nitrogen-containing aromatic heterocyclic compounds used as host materials. However, organic EL devices containing compounds disclosed in the above-described patent publications are still unsatisfactory in terms of power efficiency, luminous efficiency, lifespan, etc.

Accordingly, the inventors of the present invention conducted research to find a host compound with excellent electron transfer efficiency and found that the compound of the present invention has higher luminous efficiency than conventional organic electroluminescent compounds, and that when the compound of the present invention is used in the light-emitting layer of an organic EL device, It was found that the charge balance between holes and electrons in the light-emitting layer was well achieved, the current/power efficiency of the device was increased, and the driving voltage was lowered, resulting in a longer lifespan.

Republic of Korea Patent Publication No. 10-2013-0139916 (publication date: December 23, 2013) Republic of Korea Patent Publication No. 10-2013-0093460 (Publication date: August 22, 2013)

Therefore, the purpose of the present invention is, firstly, to provide an organic electroluminescent compound with high luminous efficiency, and secondly, to provide an organic electroluminescent device with low driving voltage and improved current/power efficiency that includes the organic electroluminescent compound in a light-emitting layer. It is provided.

As a result of intensive research to solve the above technical problems, the present inventors discovered that the compound represented by the following formula (1) achieves the above-mentioned purpose and completed the present invention.

[Formula 1]

In Formula 1,

Ring A is a substituted or unsubstituted (C6-C30) aryl ring, or a substituted or unsubstituted (5-30 membered) heteroaryl ring,

X and Y are each independently O, S, CR ₁₁ R ₁₂ or NR ₁₃ ,

L ₁ is a single bond, substituted or unsubstituted (C6-C30)arylene, or substituted or unsubstituted (5-30 membered)heteroarylene,

Ar ₁ is substituted or unsubstituted (C6-C30)aryl, or substituted or unsubstituted (5-30 membered)heteroaryl,

R ₁ and R ₂ are each independently hydrogen, deuterium, halogen, cyano, substituted or unsubstituted (C1-C30)alkyl, substituted or unsubstituted (C6-C30)aryl, substituted or unsubstituted (5- 30 members) Heteroaryl, substituted or unsubstituted (C6-C30)aralkyl, substituted or unsubstituted (C3-C30)cycloalkyl, substituted or unsubstituted (C1-C30)alkoxy, substituted or unsubstituted ( C1-C30)alkylsilyl, substituted or unsubstituted (C6-C30)arylsilyl, substituted or unsubstituted (C6-C30)ar(C1-C30)alkylsilyl, substituted or unsubstituted (C1-C30)alkyl Amino, substituted or unsubstituted (C6-C30)arylamino, or substituted or unsubstituted (C1-C30)alkyl(C6-C30)arylamino, or connected to adjacent substituents to form a (C3-C30) single ring or A polycyclic alicyclic or aromatic ring may be formed, and the carbon atoms of the formed alicyclic or aromatic ring may be replaced with one or more heteroatoms selected from nitrogen, oxygen and sulfur,

R ₁₁ and R ₁₂ are each independently substituted or unsubstituted (C1-C30)alkyl, substituted or unsubstituted (C6-C30)aryl, substituted or unsubstituted (5-30 membered)heteroaryl, substituted or unsubstituted It may be substituted (C6-C30)aralkyl, or substituted or unsubstituted (C3-C30)cycloalkyl, or may be connected to adjacent substituents to form a (C3-C30) monocyclic or polycyclic alicyclic or aromatic ring. and the carbon atom of the alicyclic or aromatic ring formed may be replaced with one or more heteroatoms selected from nitrogen, oxygen and sulfur,

R ₁₃ is substituted or unsubstituted (C1-C30)alkyl, substituted or unsubstituted (C6-C30)aryl, substituted or unsubstituted (5-30 membered)heteroaryl, substituted or unsubstituted (C6-C30) )Aralkyl, or substituted or unsubstituted (C3-C30)cycloalkyl,

a and b are integers from 0 to 4, and when a or b is 2 or more, each R ₁ or R ₂ may be the same or different,

The heteroaryl and heteroarylene include one or more heteroatoms selected from B, N, O, S, Si and P.

The organic electroluminescent compound according to the present invention can reduce the driving voltage of the device and simultaneously improve current/power efficiency.

The present invention is described in more detail below, but this is for illustrative purposes only and should not be construed as limiting the scope of the present invention.

The present invention relates to an organic electroluminescent compound represented by Formula 1, an organic electroluminescent material containing the organic electroluminescent compound, and an organic electroluminescent device containing the material.

In the compound of formula 1 of the present invention, preferably, ring A is a substituted or unsubstituted (C6-C12) aryl ring, or a substituted or unsubstituted (5-15 membered) heteroaryl ring, and X and Y are are each independently O, S, CR ₁₁ R ₁₂ or NR ₁₃ , and L ₁ is a single bond, substituted or unsubstituted (C6-C12)arylene, or substituted or unsubstituted (5-15 membered) heteroarylene. and Ar ₁ is substituted or unsubstituted (C6-C18)aryl, or substituted or unsubstituted (5-15 membered)heteroaryl, and R ₁ and R ₂ are each independently hydrogen, substituted or unsubstituted ( C1-C10)alkyl, substituted or unsubstituted (C6-C12)aryl, substituted or unsubstituted (5-15 membered)heteroaryl, substituted or unsubstituted (C6-C12)aralkyl, substituted or unsubstituted (C3-C7)cycloalkyl, substituted or unsubstituted (C1-C10)alkoxy, substituted or unsubstituted (C1-C10)alkylsilyl, substituted or unsubstituted (C6-C12)arylsilyl, substituted or unsubstituted (C6-C12)ar(C1-C10)alkylsilyl, substituted or unsubstituted (C1-C10)alkylamino, substituted or unsubstituted (C6-C12)arylamino, or substituted or unsubstituted (C1- C10)alkyl (C6-C12)arylamino, and R ₁₁ and R ₁₂ are each independently substituted or unsubstituted (C1-C10)alkyl, substituted or unsubstituted (C6-C12)aryl, substituted or unsubstituted (5-15 membered)heteroaryl, substituted or unsubstituted (C6-C12)aralkyl, or substituted or unsubstituted (C3-C7)cycloalkyl, and R ₁₃ is substituted or unsubstituted (C1-C10) Alkyl, substituted or unsubstituted (C6-C12)aryl, substituted or unsubstituted (5-15 membered)heteroaryl, substituted or unsubstituted (C6-C12)aralkyl, or substituted or unsubstituted (C3- C7) It is cycloalkyl.

In the compound of formula 1 of the present invention, more preferably, ring A is a substituted or unsubstituted (C6-C12) aryl ring, X and Y are each independently O, S or NR ₁₃ , and L ₁ is a single A bond, or a substituted or unsubstituted (C6-C12)arylene, and Ar ₁ is a substituted or unsubstituted (C6-C18)aryl, or a substituted or unsubstituted (5-15 membered) heteroaryl, and R ₁ and R ₂ are each independently hydrogen or substituted or unsubstituted (5-15 membered) heteroaryl, and R ₁₃ is substituted or unsubstituted (C6-C12) aryl.

As used herein, “(C1-C30)alkyl” refers to a straight-chain or branched-chain alkyl having 1 to 30 carbon atoms, where 1 to 20 carbon atoms are preferred, and 1 to 10 carbon atoms are more preferred. . Specific examples of the alkyl include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tert-butyl. As used herein, “(C2-C30)alkenyl” refers to straight-chain or branched-chain alkenyl having 2 to 30 carbon atoms, where 2 to 20 carbon atoms are preferred, and 2 to 10 carbon atoms are more preferred. desirable. Specific examples of the alkenyl include vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, and 2-methylbut-2-enyl. As used herein, “(C2-C30)alkynyl” refers to straight or branched chain alkynyl having 2 to 30 carbon atoms, where 2 to 20 carbon atoms are preferred, and 2 to 10 carbon atoms are more preferred. desirable. Examples of the alkynyl include ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methylpent-2-ynyl, etc. As used herein, “(C1-C30)alkoxy” means straight-chain or branched-chain alkoxy having 1 to 30 carbon atoms, where 1 to 20 carbon atoms are preferred, and 1 to 10 carbon atoms are more preferred. Examples of the alkoxy include methoxy, ethoxy, propoxy, isopropoxy, and 1-ethylpropoxy. As used herein, “(C3-C30)cycloalkyl” refers to a monocyclic or polycyclic hydrocarbon having 3 to 30 ring carbon atoms, with 3 to 20 carbon atoms being preferred, and 3 to 7 carbon atoms being more preferred. Examples of the cycloalkyl include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. As used herein, “(5-7 membered) heterocycloalkyl” has 5 to 7 ring skeleton atoms and contains one or more heteroatoms selected from the group consisting of B, N, O, S, Si and P, preferably O and S. and N, and include cycloalkyl containing one or more heteroatoms selected from N, for example, pyrrolidine, thiolane, tetrahydropyran, etc. As used herein, “(C6-C30)aryl(lene)” refers to a single ring or fused ring radical derived from an aromatic hydrocarbon having a ring skeleton of 6 to 30 carbon atoms, wherein a ring skeleton of 6 to 20 carbon atoms is preferred. , more preferably 6 to 15. Examples of the aryl include phenyl, biphenyl, terphenyl, naphthyl, fluorenyl, phenanthrenyl, anthracenyl, indenyl, triphenylenyl, pyrenyl, tetracenyl, perylenyl, chrysenyl, naphthacenyl. , fluoranthenyl, etc. As used herein, “(3-30 membered) heteroaryl (lene)” refers to an aryl group having 3 to 30 ring skeleton atoms and containing at least one heteroatom selected from the group consisting of B, N, O, S, Si and P. it means. Here, the number of ring skeleton atoms is preferably 3 to 20, and more preferably 3 to 15. The number of heteroatoms is preferably 1 to 4, and may be a single ring system or a fused ring system condensed with one or more benzene rings, and may be partially saturated. In addition, the heteroaryl herein also includes forms where one or more heteroaryl groups or aryl groups are connected to heteroaryl groups by a single bond. Examples of the heteroaryl include furyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, and tetrazinyl. , triazolyl, tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, etc. single ring heteroaryl, benzofuranyl, benzothiophenyl, isobenzofuranyl, dibenzofuranyl, di Benzothiophenyl, benzoimidazolyl, benzothiazolyl, benzoisothiazolyl, benzoisoxazolyl, benzooxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, acid There are fused ring heteroaryls such as nolinyl, quinazolinyl, quinoxalinyl, carbazolyl, phenoxazinyl, phenanthridinyl, and benzodioxolyl. As used herein, “halogen” includes F, Cl, Br and I atoms.

In addition, in the description of “substituted or unsubstituted” described herein, “substitution” means replacing a hydrogen atom in a certain functional group with another atom or another functional group (i.e., substituent). In the present invention, substituted alkyl, substituted alkenyl, substituted alkynyl, substituted cycloalkyl, substituted aryl (lene), substituted heteroaryl (lene), substituted alkoxy and substituted (C3-C30) monocyclic or polycyclic alicyclic or aromatic ring Substituents are each independently deuterium, halogen, cyano, carboxyl, nitro, hydroxy, halogen-substituted or unsubstituted (C1-C30)alkyl, (C1-C30)alkoxy, (C1-C30)alkylthio, (5-30 membered) heteroaryl-substituted or unsubstituted (C6-C30)aryl, (C6-C30)aryl-substituted or unsubstituted (5-30 membered)heteroaryl, (C3-C30)cycloalkyl, (C3-C30)cycloalkenyl, (3-7 membered)heterocycloalkyl, (C6-C30)aryloxy, (C6-C30)arylthio, tri(C1-C30)alkylsilyl, tri(C6-C30) Arylsilyl, di(C1-C30)alkyl(C6-C30)arylsilyl, (C1-C30)alkyldi(C6-C30)arylsilyl, amino, (C2-C30)alkenyl, (C2-C30)alkynyl , mono- or di(C1-C30)alkylamino, mono- or di(C6-C30)arylamino, (C1-C30)alkyl(C6-C30)arylamino, (C1-C30)alkylcarbonyl, (C1 -C30)alkoxycarbonyl, (C6-C30)arylcarbonyl, di(C6-C30)arylboronyl, di(C1-C30)alkylboronyl, (C1-C30)alkyl(C6-C30)aryl It is one or more substituents selected from the group consisting of boronyl, (C6-C30)ar(C1-C30)alkyl, and (C1-C30)alkyl(C6-C30)aryl.

Examples of organic electroluminescent compounds according to the present invention include the following compounds.

The organic electroluminescent compound according to the present invention can be prepared by a synthetic method known to those skilled in the art, for example, according to Scheme 1 below.

[Scheme 1]

In Scheme 1, X, Y, L ₁ , Ar ₁ , R ₁ , R ₂ , a, b and A ring are defined as in Formula 1, and Hal is halogen.

Additionally, the present invention provides an organic electroluminescent material containing the organic electroluminescent compound of Formula 1 and an organic electroluminescent device containing the material. The material may be composed solely of the organic electroluminescent compound of the present invention, or may additionally contain common materials included in organic electroluminescent materials.

The organic electroluminescent device according to the present invention includes a first electrode; second electrode; and one or more organic material layers interposed between the first electrode and the second electrode, wherein the organic material layer may include one or more organic electroluminescent compounds of Formula 1 of the present invention.

One of the first electrode and the second electrode may be an anode and the other may be a cathode. The organic material layer includes a light-emitting layer, and may further include one or more layers selected from a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, an interlayer, and an electron blocking layer.

The organic electroluminescent compound of the present invention may be included in the light-emitting layer. When used in the light-emitting layer, the organic electroluminescent compound of the present invention may be included as a host material.

The organic electroluminescent device containing the organic electroluminescent compound of the present invention may further include one or more other compounds other than the organic electroluminescent compound of the present invention as a host material, and may further include one or more dopants.

When the organic electroluminescent compound of the present invention is included as a host material (first host material) of the light emitting layer, other compounds may be included as the second host material. At this time, the weight ratio of the first host material and the second host material is in the range of 1:99 to 99:1.

Any known phosphorescent host can be used as the host material for compounds other than the organic electroluminescent compound of the present invention, but it is particularly preferable in terms of luminous efficiency to be selected from the group consisting of compounds represented by the following formulas 11 to 15. do.

[Formula 11]

H-(Cz-L ₄ ) _l -M

[Formula 12]

H-(Cz) _m -L ₄ -M

[Formula 13]

[Formula 14]

[Formula 15]

In Formulas 11 to 15,

Cz has the following structure,

A is -O- or -S-;

R ₂₆ to R ₂₉ are each independently hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30)alkyl, substituted or unsubstituted (C6-C30)aryl, substituted or unsubstituted (5-30 members) heteroaryl or -SiR ₃₀ R ₃₁ R ₃₂ ; R ₃₀ to R ₃₂ are each independently substituted or unsubstituted (C1-C30)alkyl, or substituted or unsubstituted (C6-C30)aryl; L ₄ is a single bond, substituted or unsubstituted (C6-C30)arylene, or substituted or unsubstituted (5-30 membered)heteroarylene; M is substituted or unsubstituted (C6-C30)aryl, or substituted or unsubstituted (5-30 membered)heteroaryl; Y ₁ and Y ₂ are -O-, -S-, -N(R ₃₃ )-, or -C(R ₃₄ )(R ₃₅ )-, and Y ₁ and Y ₂ do not exist simultaneously; R ₃₃ to R ₃₅ are each independently substituted or unsubstituted (C1-C30)alkyl, substituted or unsubstituted (C6-C30)aryl, or substituted or unsubstituted (5-30 membered) heteroaryl, R ₃₄ and R ₃₅ may be the same or different; l and m are each independently integers of 1 to 3, n, o, p and q are each independently integers of 0 to 4, and when l, m, n, o, p, or q is an integer of 2 or more, respectively (Cz-L ₄ ), each (Cz), each R ₂₆ , each R ₂₇ , each R ₂₈ or each R ₂₉ may be the same or different.

Specifically, preferred examples of the second host material are as follows.

[Here, TPS is a triphenylsilyl group]

The dopant included in the organic electroluminescent device of the present invention is preferably at least one phosphorescent dopant. The phosphorescent dopant material applied to the organic electroluminescent device of the present invention is not particularly limited, but a complex compound of a metal atom selected from iridium (Ir), osmium (Os), copper (Cu), and platinum (Pt) is preferred. And, ortho-metalated complex compounds of metal atoms selected from iridium (Ir), osmium (Os), copper (Cu), and platinum (Pt) are more preferable, and ortho-metalated iridium complex compounds are even more preferable.

The phosphorescent dopant is preferably selected from the group consisting of compounds represented by the following formulas 101 to 103.

In Formulas 101 to 103, L is selected from the following structures;

R ₁₀₀ is hydrogen, substituted or unsubstituted (C1-C30)alkyl, or substituted or unsubstituted (C3-C30)cycloalkyl;

R ₁₀₁ to R ₁₀₉ and R ₁₁₁ to R ₁₂₃ are each independently hydrogen, deuterium, halogen, halogen-substituted or unsubstituted (C1-C30)alkyl, cyano, substituted or unsubstituted (C1-C30)alkoxy, substituted or unsubstituted (C6-C30)aryl, or substituted or unsubstituted (C3-C30)cycloalkyl; R ₁₀₆ to R ₁₀₉ may be connected to adjacent substituents to form a substituted or unsubstituted (C3-C30) monocyclic or polycyclic alicyclic or aromatic ring (e.g. fluorene, dibenzothiophene, dibenzofuran). There is; R ₁₂₀ to R ₁₂₃ may be connected to adjacent substituents to form a substituted or unsubstituted (C3-C30) monocyclic or polycyclic alicyclic or aromatic ring (eg, quinoline);

R ₁₂₄ to R ₁₂₇ are each independently hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30)alkyl, or substituted or unsubstituted (C6-C30)aryl; R ₁₂₄ to R ₁₂₇ are connected to adjacent groups to form a substituted or unsubstituted (C3-C30) monocyclic or polycyclic alicyclic or (hetero) aromatic ring (e.g. fluorene, dibenzothiophene, dibenzofuran) can;

R ₂₀₁ to R ₂₁₁ are each independently hydrogen, deuterium, halogen, halogen-substituted or unsubstituted (C1-C30)alkyl, substituted or unsubstituted (C3-C30)cycloalkyl, or substituted or unsubstituted (C6) -C30) is aryl, and R ₂₀₈ to R ₂₁₁ are connected to adjacent groups to form a substituted or unsubstituted (C3-C30) monocyclic or polycyclic alicyclic or (hetero) aromatic ring (e.g. fluorene, dibenzothiophene, dibenzofuran);

r and s are each independently integers of 1 to 3, and when r or s are each integers of 2 or more, each R ₁₀₀ may be the same or different from each other;

e is an integer from 1 to 3.

Specific examples of the phosphorescent dopant material are as follows.

In a further aspect, the present invention provides a composition for manufacturing an organic electroluminescent device. The composition includes a compound of the present invention as a host material.

Additionally, the organic electroluminescent device of the present invention includes a first electrode; second electrode; and one or more organic material layers interposed between the first electrode and the second electrode, wherein the organic material layer includes a light-emitting layer, and the light-emitting layer may include the composition for an organic electroluminescent device of the present invention.

The organic electroluminescent device of the present invention includes the organic electroluminescent compound of Formula 1, and may also include one or more compounds selected from the group consisting of arylamine-based compounds and styrylarylamine-based compounds.

In addition, in the organic electroluminescent device of the present invention, in addition to the organic electroluminescent compound of Formula 1, the organic material layer contains organic metals of Group 1, Group 2, 4th period transition metals, 5th period transition metals, lanthanide series metals, and d-transition elements. It may further include one or more metals or complex compounds thereof selected from the group consisting of, and further, the organic material layer may further include a light-emitting layer and a charge generation layer.

In addition, the organic electroluminescent device of the present invention may emit white light by further including one or more light emitting layers containing blue, red, or green light emitting compounds known in the art in addition to the organic electroluminescent compound of the present invention. Additionally, if necessary, a yellow or orange light emitting layer may be further included.

In the organic electroluminescent device of the present invention, one or more layers selected from a chalcogenide layer, a metal halide layer, and a metal oxide layer are placed on at least one inner surface of a pair of electrodes (hereinafter, these are referred to as “surface layers”). It is desirable to place (refers to). Specifically, it is preferable to dispose a silicon and aluminum chalcogenide (including oxide) layer on the anode surface on the light-emitting medium layer side, and a metal halide layer or metal oxide layer on the cathode surface on the light-emitting medium layer side. The operation of the device can be stabilized by the surface layer. _Preferred examples _{of the} chalcogenide include _SiO Rare earth metals, etc., and preferred examples of metal oxides include Cs ₂ O, Li ₂ O, MgO, SrO, BaO, CaO, etc.

In addition, in the organic electroluminescent device of the present invention, it is also preferable to dispose a mixed region of an electron transport compound and a reducing dopant or a mixed region of a hole transport compound and an oxidizing dopant on at least one surface of a pair of electrodes. In this way, the electron transport compound is reduced to an anion, making it easy to inject and transport electrons from the mixed region to the light emitting medium. Additionally, since the hole transport compound is oxidized to become a cation, it becomes easy to inject and transport holes from the mixed region to the light emitting medium. Preferred oxidizing dopants include various Lewis acids and acceptor compounds, and preferred reducing dopants include alkali metals, alkali metal compounds, alkaline earth metals, rare earth metals, and mixtures thereof. Additionally, a white light-emitting organic electroluminescent device with two or more light-emitting layers can be manufactured by using a reducing dopant layer as a charge generation layer.

Each layer of the organic electroluminescent device of the present invention is formed by any one of dry film deposition methods such as vacuum deposition, sputtering, plasma, and ion plating, or wet film formation methods such as spin coating, dip coating, and flow coating. can be applied.

In the case of the wet film forming method, a thin film is formed by dissolving or dispersing the materials forming each layer in an appropriate solvent such as ethanol, chloroform, tetrahydrofuran, or dioxane, and the solvent is used to dissolve or disperse the materials forming each layer. It can be anything, as long as there is no problem with the tabernacle.

Hereinafter, for a detailed understanding of the present invention, representative compounds of the present invention will be described, including the organic electroluminescent compound according to the present invention, its manufacturing method, and the luminescence characteristics of the device containing the same.

[ Example 1] Preparation of compound H-15

compound 1-1 manufacture of

60 g (281 mmol) of 3-bromo-[ b ]benzothiophene, 4,4,4',4',5,5,5',5'-octamethyl-2,2 in a 3L round bottom flask (RBF). '-bi(1,3,2-dioxaborolane) 86g (337mmol), bis(triphenylphosphine)palladium(II) dichloride (PdCl ₂ (PPh ₃ ) ₂ ) 10g (14mmol), potassium acetate ( 69 g (704 mmol) of KOAc) and 1,400 ml of 1,4-dioxane were added, and stirred at 120°C for 4 hours. The reaction mixture was worked-up with ethyl acetate (EA)/H ₂ O, moisture was removed with MgSO ₄ , and distilled under reduced pressure. The crude product was subjected to column chromatography using methylene chloride (MC):hexane (Hx) to obtain 55 g (75%) of compound 1-1 as a white solid.

compound 1-2 manufacture of

In 3L RBF, 55g (211mmol) of compound 1-1 , 83g (296mmol) of 2,5-dibromonitrobenzene, tetrakis(triphenylphosphine)palladium(O) (Pd(PPh ₃ ) ₄ ) 12.2g (10.5) mmol), 60.5 g (570 mmol) of Na ₂ CO ₃ , 1100 ml of toluene, 285 ml of ethanol, and 285 ml of water were added and dissolved, and then stirred at 130°C for 8 hours. The reaction mixture was post-treated with EA/H ₂ O, moisture was removed with MgSO ₄ , and then distilled under reduced pressure. The crude product was subjected to column chromatography using MC:Hx to obtain 40 g (56%) of compound 1-2 as a yellow liquid.

compound 1-3 manufacture of

40 g (120 mmol) of compound 1-2 , 400 ml of triethyl phosphite, and 400 ml of 1,2-dichlorobenzene (1,2-DCB) were added to 2L RBF, and stirred at 150°C for 3 hours. The reaction mixture was distilled to obtain a solid. The crude product was subjected to column chromatography using MC:Hx to obtain 25 g (70%) of solid compound 1-3 .

compound 1-4 manufacture of

Add and dissolve 25 g (83 mmol) of compound 1-3 , 46 ml (414 mmol) of iodobenzene, 7.9 g (41 mmol) of CuI, 11 ml (165 mmol) of ethylenediamine, 52.6 g (248 mmol) of K ₃ PO ₄ and 400 ml of toluene in 2L RBF. , and stirred at 100°C for 1.5 hours. The reaction mixture was post-treated with EA/H ₂ O, moisture was removed with MgSO ₄ , and then distilled under reduced pressure. The crude product was subjected to column chromatography using MC:Hx to obtain 17 g (55%) of compound 1-4 as a white solid.

compound 1-5 manufacture of

In 1L RBF, 15g (40mmol) of compound 1-4 , 5.4ml (60mmol) of aniline, 356mg (1.6mmol) of palladium (II) acetate (Pd(OAc) ₂ ), 2-dicyclohexylphosphino-2',6' -Dimethoxybiphenyl (s-phos) 1.3g (3.2mmol), Cs ₂ CO ₃ 32.3g (100mmol) and 200ml toluene were added, and stirred at 130°C for 3 hours. The reaction mixture was post-treated with EA/H ₂ O, moisture was removed with MgSO ₄ , and then distilled under reduced pressure. The crude product was subjected to column chromatography using MC:Hx to obtain 9 g (59%) of solid compound 1-5 .

compound 1-6 manufacture of

8.5 g (22 mmol) of Compound 1-5 , 224 mg (1 mmol) of Pd(OAc) _2, 300 mg (2 mmol) of K ₂ CO ₃ and 110 ml of pivalic acid were added to 1 L RBF, and stirred at 140°C for 25 hours. The reaction mixture was added dropwise back to water and then filtered under reduced pressure. The crude product was subjected to column chromatography using MC:Hx to obtain 1.1 g (12%) of solid compound 1-6 .

compound H-15 manufacture of

In 100 mL RBF, 1 g (26 mmol) of compound 1-6 , 1.3 g (33 mmol) of 2-(4-bromophenyl)-4,6-diphenyl-1,3,5-triazine, and 30 mg (30 mg) of Pd(OAc) ₂ ( 0.13 mmol), 110 mg (0.25 mmol) of s-phos, 620 mg (6.4 mmol) of sodium tert-butoxide (NaOt-Bu), and 26 ml of toluene were added, and stirred at 120°C for 5 hours. The reaction mixture was post-treated with EA/H ₂ O, moisture was removed with MgSO ₄ , and then distilled under reduced pressure. The crude product was subjected to column chromatography using MC:Hx to obtain 1 g (50%) of compound H-15 as a solid.

[device Example 1] Organic according to the present invention electric field using luminescent compounds OLED Device fabrication

An OLED device was manufactured using the organic electroluminescent compound of the present invention. First, the transparent electrode ITO thin film (10Ω/□) on the OLED glass (manufactured by Geomatec) substrate was ultrasonic cleaned using acetone, ethanol, and distilled water sequentially, and then stored in isopropanol before use. Next, after mounting the ITO substrate on the substrate holder of the vacuum deposition equipment, HI-1 is put into the cell in the vacuum deposition equipment, the vacuum in the chamber is evacuated until the vacuum degree reaches 10 ^-6 torr, and then a current is applied to the cell. By evaporation, an 80 nm thick first hole injection layer was deposited on the ITO substrate. Next, HI-2 was placed in another cell in the vacuum deposition equipment, and a current was applied to the cell to evaporate it, thereby depositing a second hole injection layer with a thickness of 5 nm on the first hole injection layer. Next, HT-1 was placed in a cell in the vacuum deposition equipment, and a current was applied to the cell to evaporate it to deposit a 10 nm thick first hole transport layer on the second hole injection layer. HT-2 was placed in another cell in the vacuum deposition equipment, and a current was applied to the cell to evaporate it to deposit a second hole transport layer with a thickness of 60 nm on the first hole transport layer. After forming the hole injection layer and hole transport layer, the light emitting layer was deposited on them as follows. Compound H-15 was put into one cell of the vacuum deposition equipment as a host, and compound D-96 was put into another cell as a dopant. Then, the two materials were evaporated at different rates to give the dopant relative to the total amount of the host and dopant. A 40 nm thick light emitting layer was deposited on the second hole transport layer by doping it in an amount of 3% by weight. Subsequently, ET-1 and EI-1 were evaporated at a rate of 1:1 in two other cells to deposit a 30 nm thick electron transport layer on the light emitting layer. Subsequently, EI-1 was deposited to a thickness of 2 nm as an electron injection layer, and then an Al cathode was deposited to a thickness of 80 nm using another vacuum deposition equipment to manufacture an OLED device.

As a result, an efficiency of 17.8 cd/A was shown at a voltage of 4.6 V, red light emission of 5000 cd/m ² was confirmed, and the minimum time taken for the light emission to drop to 75% at a brightness of 5000 nit was 14 hours.

[ Comparative example 1] Conventional Organic electric field using luminescent compounds OLED device manufacturing

An OLED device was manufactured in the same manner as Device Example 1, except that Compound X below was used as a host as a light emitting material.

As a result, it showed an efficiency of 13.8 cd/A at a voltage of 12.4 V, red light emission of 5000 cd/m ² was confirmed, and it took 4 hours for the light emission to drop to 75% at a brightness of 5000 nit.

The organic electroluminescent compound according to the present invention has superior luminous efficiency and a long operating life compared to conventional organic electroluminescent compounds. Additionally, devices using the organic electroluminescent compound according to the present invention have excellent luminescence characteristics, especially current/power efficiency.

Claims (6)

An organic electroluminescent compound represented by the following formula (1).
[Formula 1]

In Formula 1,
Ring A is a substituted or unsubstituted (C6-C30) aryl ring,
X and Y are each independently O, S or NR ₁₃ ,
L ₁ is a single bond, substituted or unsubstituted (C6-C30)arylene, or substituted or unsubstituted (5-30 membered)heteroarylene,
Ar ₁ is substituted or unsubstituted (C6-C30)aryl, or substituted or unsubstituted (5-30 membered) heteroaryl, excluding phenyl substituted with diphenylamino,
R ₁ and R ₂ are each independently hydrogen, deuterium, halogen, cyano, substituted or unsubstituted (C1-C30)alkyl, substituted or unsubstituted (C6-C30)aryl, substituted or unsubstituted (5- 30 members) Heteroaryl, substituted or unsubstituted (C6-C30)aralkyl, substituted or unsubstituted (C3-C30)cycloalkyl, substituted or unsubstituted (C1-C30)alkoxy, substituted or unsubstituted ( C1-C30)alkylsilyl, substituted or unsubstituted (C6-C30)arylsilyl, substituted or unsubstituted (C6-C30)ar(C1-C30)alkylsilyl, substituted or unsubstituted (C1-C30)alkyl Amino, substituted or unsubstituted (C6-C30)arylamino, or substituted or unsubstituted (C1-C30)alkyl(C6-C30)arylamino, or connected to adjacent substituents to form a (C3-C30) monocyclic or A polycyclic alicyclic or aromatic ring may be formed, and the carbon atoms of the formed alicyclic or aromatic ring may be replaced with one or more heteroatoms selected from nitrogen, oxygen and sulfur,
R ₁₃ is substituted or unsubstituted (C1-C30)alkyl, substituted or unsubstituted (C6-C30)aryl, substituted or unsubstituted (5-30 membered)heteroaryl, substituted or unsubstituted (C6-C30) )Aralkyl, or substituted or unsubstituted (C3-C30)cycloalkyl,
a and b are integers from 0 to 4, and when a or b is 2 or more, each R ₁ or R ₂ may be the same or different,
The heteroaryl and heteroarylene include one or more heteroatoms selected from B, N, O, S, Si and P,
However, except for the case where Formula 1 has the following structure,

Except in the case where A is a benzene ring, L ₁ is a single bond, and Ar ₁ is benzoquinazolinyl substituted with phenyl, or unsubstituted naphthyl,
When A is a benzene ring and Y is NR ₁₃ , L ₁ is a single bond or phenylene, and Ar ₁ is diphenyltriazinyl; or L ₁ is a single bond and Ar ₁ is quinazolinyl substituted with phenyl or quinazolinyl substituted with naphthylphenyl,
When A is a benzene ring and Y is NR ₁₃ , except for the case where L ₁ is a single bond and Ar ₁ is unsubstituted phenyl,
When A is a benzene ring, Y is NR ₁₃ , and R ₁₃ is phenyl, L ₁ is a single bond, and Ar ₁ is diphenylpyrimidinyl, unsubstituted biphenyl, or unsubstituted terphenyl, except do,
When A is a benzene ring, Y is NR ₁₃ , and R ₁₃ is phenyl, except for the case where L ₁ is phenylene and Ar ₁ is quinazolinyl substituted with phenyl, or benzoquinazolinyl substituted with phenyl do,
The following compounds are excluded.

The method of claim 1, wherein in Formula 1, the substituents of substituted alkyl, substituted cycloalkyl, substituted aryl (lene), substituted heteroaryl (lene), and substituted alkoxy are each independently selected from deuterium, halogen, cyano, carboxyl, and nitro. , hydroxy, halogen-substituted or unsubstituted (C1-C30)alkyl, (C1-C30)alkoxy, (C1-C30)alkylthio, (5-30 membered) heteroaryl-substituted or unsubstituted (C6- C30)aryl, (C6-C30)aryl-substituted or unsubstituted (5-30 membered)heteroaryl, (C3-C30)cycloalkyl, (C3-C30)cycloalkenyl, (3-7 membered)heterocyclo Alkyl, (C6-C30)aryloxy, (C6-C30)arylthio, tri(C1-C30)alkylsilyl, tri(C6-C30)arylsilyl, di(C1-C30)alkyl(C6-C30)arylsilyl , (C1-C30)alkyldi(C6-C30)arylsilyl, amino, (C2-C30)alkenyl, (C2-C30)alkynyl, mono or di(C1-C30)alkylamino, mono or di(C6) -C30)arylamino, (C1-C30)alkyl(C6-C30)arylamino, (C1-C30)alkylcarbonyl, (C1-C30)alkoxycarbonyl, (C6-C30)arylcarbonyl, di(C6) -C30)arylboronyl, di(C1-C30)alkylboronyl, (C1-C30)alkyl(C6-C30)arylboronyl, (C6-C30)ar(C1-C30)alkyl and (C1 An organic electroluminescent compound, which is at least one selected from the group consisting of -C30)alkyl(C6-C30)aryl. The method of claim 1, wherein ring A is a substituted or unsubstituted (C6-C12) aryl ring, X and Y are each independently O, S or NR ₁₃ , and L ₁ is a single bond, substituted or unsubstituted ( C6-C12)arylene, or substituted or unsubstituted (5-15 membered) heteroarylene, and Ar ₁ is substituted or unsubstituted (C6-C18)aryl, or substituted or unsubstituted (5-15 membered) ) heteroaryl, and R ₁ and R ₂ are each independently hydrogen, substituted or unsubstituted (C1-C10)alkyl, substituted or unsubstituted (C6-C12)aryl, substituted or unsubstituted (5-15 members) ) Heteroaryl, substituted or unsubstituted (C6-C12)aralkyl, substituted or unsubstituted (C3-C7)cycloalkyl, substituted or unsubstituted (C1-C10)alkoxy, substituted or unsubstituted (C1- C10)alkylsilyl, substituted or unsubstituted (C6-C12)arylsilyl, substituted or unsubstituted (C6-C12)ar(C1-C10)alkylsilyl, substituted or unsubstituted (C1-C10)alkylamino, Substituted or unsubstituted (C6-C12)arylamino, or substituted or unsubstituted (C1-C10)alkyl(C6-C12)arylamino, and R ₁₃ is substituted or unsubstituted (C1-C10)alkyl, substituted or unsubstituted (C6-C12)aryl, substituted or unsubstituted (5-15 membered)heteroaryl, substituted or unsubstituted (C6-C12)aralkyl, or substituted or unsubstituted (C3-C7)cyclo. Alkylin, organic electroluminescent compound. _The method of claim 1, wherein ring A is a substituted or unsubstituted (C6-C12) _aryl ring, (C6-C12)arylene, Ar ₁ is substituted or unsubstituted (C6-C18)aryl, or substituted or unsubstituted (5-15 membered) heteroaryl, and R ₁ and R ₂ are each independently hydrogen , or a substituted or unsubstituted (5-15 membered) heteroaryl, and R ₁₃ is a substituted or unsubstituted (C6-C12)aryl. The organic electroluminescent compound according to claim 1, wherein the compound represented by Formula 1 is selected from the following compounds.

An organic electroluminescent device comprising the organic electroluminescent compound according to claim 1.