KR20160070395A - Organic Electroluminescent Compound and Organic Electroluminescent Device Comprising the Same - Google Patents

Abstract

The present invention relates to an organic electroluminescent compound and an organic electroluminescent device comprising the same. By comprising the organic electroluminescent compound, the organic electroluminescent device can embody colors having high purity and improved operating life while having low operating voltage and excellent light emitting efficiency such as current efficiency and power efficiency. The organic electroluminescent compound is represented by chemical formula 1.

Description

TECHNICAL FIELD [0001] The present invention relates to an organic electroluminescent compound and an organic electroluminescent compound including the same,

The present invention relates to an organic electroluminescent compound and an organic electroluminescent device including the same.

Among display devices, an electroluminescent device (EL device) is a self-luminous display device having a wide viewing angle, an excellent contrast, and a high response speed. In 1987, Eastman Kodak Company developed an organic EL device using an aromatic diamine and an aluminum complex having low molecular weight as a light emitting layer forming material [Appl. Phys. Lett. 51, 913, 1987].

The most important factor determining the luminous efficiency in an organic electroluminescent device is a light emitting material. Fluorescent materials have been widely used as luminescent materials to date, but the development of phosphorescent materials has been widely studied in that phosphorescent materials can improve luminous efficiency up to 4 times the theoretical efficiency of phosphorescent materials in terms of the mechanism of electroluminescence . Until now, an iridium (III) complex series has been widely known as a phosphorescent material. Each RGB has bis (2- (2'-benzothienyl) -pyridinate-N, C-3 ') iridium (acetylacetonate ) [(acac) Ir (btp ) 2], tris (2-phenylpyridine) iridium [Ir (ppy) _3] and the bis (4,6-difluorophenyl pyridinyl Nei Sat -N, C2) avoid collision Ney And materials such as tolidium (Firpic) are known.

In the prior art, 4,4'-N, N'-dicarbazole-biphenyl (CBP) is the most widely known phosphorescent host material. In recent years, Pioneer et al. Of Japan have been using bathocuproine (BCP) and aluminum (III) bis (2-methyl-8-quinolinate) (4-phenyl phenolate) Balq) as a host material and developed a high-performance organic electroluminescent device.

However, existing materials are advantageous in terms of luminescent properties, but they have the following disadvantages: (1) the material is changed when the glass transition temperature is low and the thermal stability is low and the material is subjected to a high temperature deposition process under vacuum. (2) In the organic electroluminescent device, the power efficiency is in the relation of [(? / Voltage) x current efficiency], so that the power efficiency is inversely proportional to the voltage. In the organic electroluminescent device using the phosphorescent host material, The current efficiency (cd / A) is higher than that of the light emitting device, but the driving voltage is also very high, so there is no great advantage in terms of power efficiency (lm / w). (3) In addition, when used in an organic electroluminescent device, it is unsatisfactory in terms of operating life, and luminous efficiency is still required to be improved.

N, N ', N'-diphenyl-N'-phenylamino) biphenyl (NPB) as a hole injecting and transporting material in an organic electroluminescent device, (TPD), 4,4 ', 4 "-tris (3-methylphenylphenyl) -4,4'-diamine Amino) triphenylamine (MTDATA). However, when such a material is used, the organic electroluminescent device has a problem of deteriorating quantum efficiency and lifetime because the organic electroluminescent device is driven at a high current, Since the thermal stress is generated between the anode and the hole injection layer and the lifetime of the device is rapidly lowered due to the thermal stress. Further, since the organic material used for the hole injection layer has a high hole mobility , The hole-electron charge balance of holes and electrons is broken and the quantum efficiency (cd / A) is lowered The.

Japanese Laid-Open Patent Publication No. 2013-93432 discloses a carbazole or biscarbazole-based compound having a triphenylsilyl group. However, a compound in which a nitrogen-containing heteroaryl or aryl is connected to the N atom of one carbazole of the biscarbazole skeleton and a heteroaryl or aryl substituted with a silyl group is attached to the N atom of the other carbazole is not disclosed .

[ Patent Literature ]

(Patent Document 1) Japanese Laid-Open Patent Publication No. 2013-93432 (published on May 16, 2013)

An object of the present invention is to provide an organic electroluminescent compound capable of producing an organic electroluminescent device having a long driving lifetime, low driving voltage, excellent luminous efficiency and color purity such as current efficiency and power efficiency, And an organic electroluminescent compound comprising the organic electroluminescent compound.

As a result of intensive studies to solve the above technical problems, the present inventors have found that an organic electroluminescent compound represented by the following general formula (1) achieves the above-mentioned object and completed the present invention.

[Chemical Formula 1]

In Formula 1,

Ar ₁ is substituted or unsubstituted nitrogen (N) (5-30 membered) heteroaryl, or substituted or unsubstituted (C 6 -C 30) aryl;

Ar ₂ and Ar ₃ are each independently substituted or unsubstituted (5-30 membered) heteroaryl, or substituted or unsubstituted (C 6 -C 30) aryl;

L ₁ is a single bond, substituted or unsubstituted (C6-C30) arylene, or substituted or unsubstituted (3-30 membered) heteroarylene;

R ₁ to R ₄ are each independently hydrogen, deuterium, halogen, cyano, carboxyl, nitro, hydroxy, substituted or unsubstituted (C 1 -C 30) alkyl, substituted or unsubstituted (C 3 -C 30) , Substituted or unsubstituted (C3-C30) cycloalkenyl, substituted or unsubstituted (3-7 membered) heterocycloalkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (3- 30 membered) heteroaryl, a substituted or unsubstituted mono (C6-C30) arylamino, a substituted or unsubstituted mono- (C1-C30) alkylamino, -NR ₅ R ₆ or or -SiR ₇ R ₈ R _9, adjacent (C3-C30) monocyclic or polycyclic alicyclic or aromatic ring optionally substituted with a substituent;

R ₅ to R ₉ are each independently substituted or unsubstituted (C 1 -C 30) alkyl, substituted or unsubstituted (C 6 -C 30) aryl, or substituted or unsubstituted (3-30 membered) heteroaryl;

The carbon atom of the alicyclic or aromatic ring may be replaced by one or more heteroatoms selected from nitrogen, oxygen and sulfur;

Wherein said heteroaryl and said heterocycloalkyl comprise at least one heteroatom selected from B, N, O, S, P (= O), Si and P;

a and d are each independently an integer of 1 to 4; When a or d is an integer of 2 or more, each R ₁ or R ₄ may be the same or different;

b and c are each independently an integer of 1 to 3; When b or c is an integer of 2 or more, each R ₂ or R ₃ may be the same or different.

The organic electroluminescent compound according to the present invention can provide an organic electroluminescent device having a low driving voltage, a high luminous efficiency such as a current efficiency and a power efficiency, and a high color purity and a long driving life.

The present invention will now be described in more detail, but this should not be construed as limiting the scope of the present invention.

As used herein, "(C1-C30) alkyl" means straight chain or branched chain alkyl having 1 to 30 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms. Specific examples of the alkyl include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert-butyl. The term "(C3-C30) cycloalkyl" means a monocyclic or polycyclic hydrocarbon having 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms, more preferably 3 to 7 carbon atoms. Examples of the cycloalkyl include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like. The "(3-7 membered) heterocycloalkyl" refers to a heterocycloalkyl group having 3 to 7 ring skeletal atoms and at least one heteroatom selected from the group consisting of B, N, O, S, P (= O) Means a cycloalkyl comprising one or more heteroatoms selected from O, S and N and includes, for example, tetrahydrofuran, pyrrolidine, thiolane, tetrahydropyran and the like. Means a single ring or fused ring radical derived from an aromatic hydrocarbon having 6 to 30 carbon atoms, wherein the number of carbon atoms in the ring skeleton is preferably 6 to 20, more preferably 6 to 15 Personal is more desirable. Examples of the aryl include phenyl, biphenyl, terphenyl, naphthyl, binaphthyl, phenylnaphthyl, naphthylphenyl, fluorenyl, phenylfluorenyl, benzofluorenyl, dibenzofluorenyl, Naphthacenyl, fluoranthenyl, and the like, as well as the naphthyl group, the naphthyl group, the naphthyl group, the naphthyl group, the naphthyl group, the naphthyl group, "(3-30) or (5-30) heteroaryl" means that the number of atoms of the ring skeleton is 3 to 30 or 5 to 30, preferably 5 to 20, and B, N, O, S , P (= O), Si and P, preferably one or more heteroatoms selected from N, O and S. The number of heteroatoms is preferably 1 to 4, and may be a monocyclic ring system or a fused ring system condensed with at least one benzene ring, and may be partially saturated. In addition, the heteroaryl (phenylene) also includes a heteroaryl group in which at least one heteroaryl or aryl group is linked to a heteroaryl group by a single bond. Examples of such heteroaryls include furyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl , Monocyclic heteroaryl such as triazolyl, tetrazolyl, furanzyl, pyridyl, pyrazinyl, pyrimidinyl and pyridazinyl, benzofuranyl, benzothiophenyl, isobenzofuranyl, dibenzofuranyl, di Benzothiazolyl, benzothiazolyl, benzothiazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, benzothiazolyl, benzothiazolyl, benzothiazolyl, benzothiazolyl, , Fused ring heteroaryl such as isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, carbazolyl, phenoxaphyl, phenanthridinyl, benzodioxolyl and the like. "Halogen" includes F, Cl, Br, and I atoms.

In the context of the term "substituted or unsubstituted" herein, "substituted" means that a hydrogen atom in a functional group is replaced by another atom or another functional group (ie, a substituent). Substituted monoalkylamines, substituted monoalkylamines, and substituted mono- or poly-substituted mono- or poly-substituted mono- or poly-substituted mono- or poly-substituted monoalkylamines, (C 1 -C 30) alkyl, (C 1 -C 30) alkoxy, (C 1 -C 30) alkoxy, (C 1 -C 30) alkoxy, (C6-C30) alkylthio, (C3-C30) cycloalkyl, (3-7 membered heterocycloalkyl, (C6-C30) aryloxy, (C6-C30) aryl, tri (C1-C30) alkylsilyl, tri (C6-C30) arylsilyl, unsubstituted (3-30 membered) heteroaryl, (3-30 membered) heteroaryl- (C1-C30) alkylsilyl, amino, 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) aryl (C6-C30) aryl (C6-C30) aryl (C1-C30) alkyl and (C1-C30) alkyl (C6-C30) aryl.

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

The organic electroluminescent compound represented by Formula 1 of the present invention will be described in detail as follows.

The compound of formula (1) may be represented by any one of the following formulas (2) to (5)

[Chemical Formula 2] < EMI ID =

[Chemical Formula 4]

In the above formulas 2 to 5,

Ar ₁ to Ar ₃ , L ₁ , and R ₁ to R ₄ are as defined in Formula 1 above.

Specifically, the compound of formula (1) may be represented by formula (2).

Wherein Ar ₁ is preferably a substituted or unsubstituted (C6-C30) aryl; More preferably (C6-C18) aryl which is unsubstituted or substituted by (C1-C10) alkyl or (C6-C18) aryl. Specifically, Ar ₁ may be substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted terphenyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted Substituted or unsubstituted phenanthrenyl, substituted or unsubstituted tetracenyl, substituted or unsubstituted triphenylenyl, substituted or unsubstituted creicenyl, substituted or unsubstituted pyrenyl, substituted or unsubstituted phenylnaphthyl, Unsubstituted naphthylphenyl, substituted or unsubstituted fluorenyl, or substituted or unsubstituted spirobifluorenyl. More specifically, Ar < ₁ > may be selected from among the following formulas:

(* In the above formula represents the connecting position).

Ar ₂ is preferably substituted or unsubstituted (5-20 membered) heteroaryl or substituted or unsubstituted (C6-C20) aryl; More preferably substituted or unsubstituted (C6-C20) aryl; (C6-C18) aryl optionally substituted with (C1-C10) alkyl, (C6-C18) aryl or (5-12 member) heteroaryl. Specifically, Ar ₂ is selected from substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted terphenyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted Substituted or unsubstituted phenanthrenyl, substituted or unsubstituted tetracenyl, substituted or unsubstituted triphenylenyl, substituted or unsubstituted creicenyl, substituted or unsubstituted pyrenyl, substituted or unsubstituted phenylnaphthyl, Unsubstituted naphthylphenyl, or substituted or unsubstituted fluorenyl. Specifically, the substituent of the group substituted at Ar ₂ is (C 1 -C 6) alkyl, phenyl, biphenyl, naphthyl, terphenyl, anthracenyl, phenanthrenyl, tetracenyl, triphenylenyl, Phenyl, naphthyl, naphthylphenyl, pyridyl, or pyrimidyl.

Ar ₃ is preferably substituted or unsubstituted (5-20 membered) heteroaryl or substituted or unsubstituted (C 6 -C 20) aryl; More preferably substituted or unsubstituted (C6-C20) aryl; (C6-C18) aryl optionally substituted with (C1-C6) alkyl. Specifically, Ar ₃ is specifically substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, or substituted or unsubstituted naphthyl; More specifically, it may be phenyl.

Specifically, * -Ar ₂ -Si (Ar ₃ ) ₃ of the above formula (1) may be selected from the following formulas:

(* In the above formula represents the connecting position, and Ph represents phenyl.)

L ₁ is preferably a single bond, substituted or unsubstituted (C6-C20) arylene, or substituted or unsubstituted (5-20 membered heteroarylene); More preferably a single bond, or a substituted or unsubstituted (C6-C20) arylene; And even more preferably (C6-C18) arylene substituted or unsubstituted with (C1-C10) alkyl or (C6-C18) aryl. Specifically, L ₁ is a substituted or unsubstituted phenylene, substituted or unsubstituted biphenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted terphenylene, substituted or unsubstituted anthracenylene , Substituted or unsubstituted phenanthrenylene, substituted or unsubstituted tetracenylene, substituted or unsubstituted triphenylenylene, substituted or unsubstituted pyrenylene, substituted or unsubstituted pyrenylene, substituted or unsubstituted pyrenylene, Substituted phenylnaphthylene, substituted or unsubstituted naphthylphenylene, or substituted or unsubstituted fluorenylene.

Specifically, L < ₁ > may be selected from the following formula:

(* In the above formula represents the connecting position).

Each of R ₁ to R ₄ is independently hydrogen, substituted or unsubstituted (C 1 -C 20) alkyl, substituted or unsubstituted (C 5 -C 20) cycloalkyl, substituted or unsubstituted (3-7 Substituted or unsubstituted (C6-C20) aryl, or substituted or unsubstituted (5-20 membered heteroaryl) or (C3-C20) monocyclic ring substituted or unsubstituted with adjacent substituents, Or a polycyclic alicyclic or aromatic ring. Specifically, R ₂ and R ₃ are hydrogen; Wherein R ₁ and R ₄ are each independently selected from the group consisting of hydrogen, substituted or unsubstituted (C 1 -C 20) alkyl, substituted or unsubstituted (C 6 -C 20) aryl, or substituted or unsubstituted (5-20 membered) Lt; / RTI >

According to one embodiment of the present invention, Ar ₁ is substituted or unsubstituted (C 6 -C 30) aryl; Ar ₂ and Ar ₃ are each independently substituted or unsubstituted (5-20 membered) heteroaryl or substituted or unsubstituted (C 6 -C 20) aryl; Wherein L < _{1 >} is a single bond, substituted or unsubstituted (C6-C20) arylene, or substituted or unsubstituted (5-20 membered) heteroarylene; Wherein each of R ₁ to R ₄ is independently hydrogen, substituted or unsubstituted (C 1 -C 20) alkyl, substituted or unsubstituted (C 5 -C 20) cycloalkyl, substituted or unsubstituted (3-7 membered) (C3-C20) monocyclic or polycyclic (C1-C20) alkyl, substituted or unsubstituted aryl, or substituted or unsubstituted (5-20 membered heteroaryl) Alicyclic or aromatic ring.

The organic electroluminescent compound of the present invention may be more specifically exemplified by the following compounds, but is not limited thereto.

The organic electroluminescent compound according to the present invention can be prepared by a synthesis method known to a person skilled in the art and can be prepared, for example, as shown in the following Reaction Scheme 1.

[Reaction Scheme 1]

In the above Reaction Scheme 1, Ar ₁ To Ar ₃ , L ₁ , R ₁ to R ₄ , a to d are the same as defined in formula (1), and Hal is halogen.

The present invention also provides an organic electroluminescent material comprising an organic electroluminescent compound of Formula 1 and an organic electroluminescent device comprising the same.

The organic electroluminescent material may be composed of the organic electroluminescent compound of the present invention alone, and may further include conventional materials included in the organic electroluminescent material.

The organic electroluminescent material may preferably be a hole transporting material or a host material, more preferably a hole transporting material. When the organic electroluminescent material is used as a host material, it may further include a second host material described below in addition to the compound of formula (1).

An organic electroluminescent device according to the present invention includes a first electrode; A second electrode; And at least one organic compound layer interposed between the first electrode and the second electrode, and the organic compound layer may include one or more compounds of the formula (1).

One of the first electrode and the second electrode may be an anode and the other may be a cathode. The organic layer may include a light emitting layer. In addition to the light emitting layer, the organic material layer may 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, a hole blocking layer, an electron blocking layer, As shown in FIG.

The compound of Formula 1 of the present invention may be included in at least one of the light emitting layer and the hole transporting layer. When the compound of Formula 1 of the present invention is used in the light emitting layer, the compound of the present invention can be included as a host material, preferably as a phosphorescent host material. When the compound of Chemical Formula 1 of the present invention is used in the light emitting layer, preferably, the light emitting layer may further include at least one dopant, and if necessary, And may be further included as a host material. When the compound of Formula 1 of the present invention is used in a hole transporting layer, the organic electroluminescent compound of the present invention may be included as a hole transporting material. When the compound of Formula 1 of the present invention is used in a hole transporting layer, the light emitting layer may include a compound of Formula 1 of the present invention as a host material, or may include a host material known in the art, have.

The host material known in the art, which is not the compound of Formula 1 when the second host material or the compound of Formula 1 of the present invention is used in the hole transporting layer when the compound of Formula 1 is used in the light emitting layer of the present invention, Any phosphorescent host can be used, but it is particularly preferable from the viewpoint of luminous efficiency that it is selected from the group consisting of the compounds represented by the following formulas (11) to (15).

(11)

_{H- (Cz-L 4) h} -M

[Chemical Formula 12]

H- (Cz) _i -L ₄ -M

[Chemical Formula 13]

[Chemical Formula 14]

[Chemical Formula 15]

In the above Formulas 11 to 15,

Cz has the following structure,

A is -O- or -S-,

R ₂₁ to R ₂₄ each independently represent hydrogen, deuterium, halogen, substituted or unsubstituted (C 1 -C 30) alkyl, substituted or unsubstituted (C 6 -C 30) aryl, substituted or unsubstituted Heteroaryl or R ₂₅ R ₂₆ R ₂₇ Si-, R ₂₅ to R ₂₇ are each independently substituted or unsubstituted (C 1 -C 30) alkyl, or substituted or unsubstituted (C 6 -C 30) aryl; L ₄ is a single bond, substituted or unsubstituted (C6-C30) arylene, or substituted or unsubstituted (5-30 membered) heteroarylene; M is a substituted or unsubstituted (C6-C30) aryl, or a substituted or unsubstituted (5-30 membered) heteroaryl; Y ₁ and Y ₂ are each independently -O-, -S-, -N (R ₃₁ ) -, or -C (R ₃₂ ) (R ₃₃ ) -, and when Y ₁ and Y ₂ are not present at the same time No; R ₃₁ to R ₃₃ are each independently a substituted or unsubstituted (C 1 -C 30) alkyl, a substituted or unsubstituted (C 6 -C 30) aryl, or a substituted or unsubstituted (5-30 membered) ₃₂ and R ₃₃ may be the same or different; each of h and i is independently an integer of 1 to 3, j, k, l and m are each independently an integer of 0 to 4, and when h, i, j, k, l or m is an integer of 2 or more, (Cz-L ₄ ), each (Cz), each R ₂₁ , each R ₂₂ , each R _23, or each R ₂₄ may be the same or different.

Specifically, preferred examples of the compounds represented by the above formulas (11) to (15) are as follows.

Wherein TPS is triphenylsilyl.

The dopant is preferably at least one phosphorescent dopant. The phosphorescent dopant material to be 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) And more preferably an ortho-metallated complex compound of a metal atom selected from iridium (Ir), osmium (Os), copper (Cu) and platinum (Pt), and still more preferably an orthometallated iridium complex compound.

As the dopant included in the organic electroluminescent device of the present invention, compounds represented by the following formulas (101) to (103) may be used.

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

R ₁₀₀ is hydrogen, substituted or unsubstituted (C 1 -C 30) alkyl, or substituted or unsubstituted (C 3 -C 30) cycloalkyl;

R ₁₀₁ to R ₁₀₉ and R ₁₁₁ to R ₁₂₃ are each independently selected from the group consisting of hydrogen, deuterium, halogen, (C 1 -C 30) alkyl, cyano, substituted or unsubstituted (C 1 -C 30) alkoxy, Substituted or unsubstituted (C6-C30) aryl, or substituted or unsubstituted (C3-C30) cycloalkyl; R ₁₀₆ to R ₁₀₉ may form a fused ring in which adjacent substituents are connected to each other to form a substituted or unsubstituted fused ring, for example, fluorene substituted or unsubstituted with alkyl, dibenzothiophene substituted or unsubstituted with alkyl, Or dibenzofuran which is substituted or unsubstituted with alkyl is possible; R ₁₂₀ to R ₁₂₃ may form a fused ring in which adjacent substituents are connected to each other to form a substituted or unsubstituted fused ring, for example, quinoline substituted or unsubstituted with alkyl or aryl;

R ₁₂₄ to R ₁₂₇ are each independently hydrogen, deuterium, halogen, substituted or unsubstituted (C 1 -C 30) alkyl, or substituted or unsubstituted (C 6 -C 30) aryl; R ₁₂₄ to R ₁₂₇ may form a fused ring in which adjacent substituents are connected to each other to form a substituted or unsubstituted fused ring, for example, fluorene substituted or unsubstituted with alkyl, dibenzothiophene substituted or unsubstituted with alkyl, Or dibenzofuran which is substituted or unsubstituted with alkyl is possible;

R ₂₀₁ to R ₂₁₁ each independently represents hydrogen, deuterium, halogen, (C 1 -C 30) alkyl substituted or unsubstituted with halogen, substituted or unsubstituted (C 3 -C 30) cycloalkyl, or substituted or unsubstituted -30) aryl, and R < ₂₀₈ &_gt; to R < ₂₁₁ &_gt; may form a fused ring in which adjacent substituents are connected to each other to form a substituted or unsubstituted fused ring. For example, fluorine, substituted or unsubstituted alkyl, Substituted dibenzothiophene or alkyl substituted or unsubstituted dibenzofuran;

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

and e is an integer of 1 to 3.

Specific examples of the dopant material are as follows.

The present invention provides, in a further aspect, a mixture or composition for the production of an organic electroluminescent device. The mixture or composition comprises a compound of the present invention. The mixture or composition may be a mixture or a composition for preparing a light emitting layer or a hole transporting layer of an organic electroluminescent device. The mixture or composition for preparing a light emitting layer of the organic electroluminescent device may be a mixture or a composition for preparing a phosphorescent light emitting layer. When the compound of the present invention is contained in a mixture or composition for producing a light emitting layer of an organic electroluminescent device, the compound of the present invention can be included as a host material. When the compound of the present invention is included as a host material, the mixture or composition may further comprise a second host material, wherein the weight ratio of the first host material to the second host material is in the range of 1:99 to 99: 1. As the second host material, those represented by the above-mentioned general formulas (11) to (15) may be used. When the compound of the present invention is contained in a mixture or composition for producing a hole transporting layer of an organic electroluminescent device, the compound of the present invention can be included as a hole transporting material.

Further, the organic electroluminescent device of the present invention includes a first electrode; A second electrode; And at least one organic material layer interposed between the first electrode and the second electrode, wherein the organic material layer includes a light emitting layer and a hole transporting layer, and at least one of the light emitting layer and the hole transporting layer is formed on the organic electroluminescent device ≪ / RTI > or mixtures thereof.

The organic electroluminescent device of the present invention includes the organic electroluminescent compound of Formula 1, and at the same time, may include at least one compound selected from the group consisting of an arylamine-based compound and a styrylarylamine-based compound.

Further, in the organic electroluminescent device of the present invention, in addition to the organic electroluminescent compound of Formula 1, an organic electroluminescent compound of the group 1, 2, 4, 5 period transition metal, lanthanide series and d- The organic compound layer may further include at least one metal or complex compound selected from the group consisting of a light emitting layer and a charge generating layer.

In addition, the organic electroluminescent device of the present invention may emit white light by including at least one light emitting layer containing a blue, red or green light emitting compound known in the art. Further, if necessary, it may further include a yellow or orange light emitting layer.

In the organic electroluminescent device of the present invention, one layer selected from a chalcogenide layer, a metal halide layer and a metal oxide layer (hereinafter referred to as "surface layer ") is formed on the inner surface of at least one of the pair of electrodes, Or more. Concretely, it is preferable to dispose a halogenated metal layer or a metal oxide layer on the surface of the anode on the side of the light emitting medium layer and on the surface of the cathode on the side of the light emitting medium layer, with a chalcogenide (including oxide) layer of a metal of silicon and aluminum Do. Thus, stabilization of the drive can be obtained. Preferred examples of the chalcogenide include SiO _x (1? _X ? 2), AlO _x (1? _X ? 1.5), SiON or SiAlON, and preferred examples of the halogenated metal include LiF, MgF ₂ , CaF ₂ , rare earth fluoride metals, Examples include Cs ₂ O, Li ₂ O, MgO, SrO, BaO, CaO, and the like.

Further, in the organic electroluminescent device of the present invention, a mixed region of the electron transfer compound and the reducing dopant, or a mixed region of the hole transport compound and the oxidative dopant, may be disposed on at least one surface of the pair of electrodes thus manufactured desirable. In this way, since the electron transfer compound is reduced to an anion, it becomes easy to inject and transfer electrons from the mixed region to the light emitting medium. Further, since the hole transport compound is oxidized and becomes a cation, it becomes easy to inject and transport holes from the mixed region into 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. Also, a white organic electroluminescent device having two or more light emitting layers can be manufactured using a reducing dopant layer as a charge generating layer.

The formation of the respective layers of the organic electroluminescent device of the present invention can be performed by a dry film formation method such as vacuum deposition, sputtering, plasma or ion plating, ink jet printing, nozzle printing, slot coating, , Spin coating, dip coating, and flow coating may be used.

In the case of the wet film formation method, a thin film is formed by dissolving or dispersing a material forming each layer in an appropriate solvent such as ethanol, chloroform, tetrahydrofuran, dioxane, etc., And it may be any thing that does not have a problem in the tabernacle.

Further, it is possible to manufacture a display device or a lighting device using the organic electroluminescent device of the present invention.

Hereinafter, the organic electroluminescent compound according to the present invention, the method for producing the same, and the luminescent characteristics of the device will be described with reference to the representative compound of the present invention for a detailed understanding of the present invention.

[ Example  1] Preparation of compound C-8

Preparation of Compound 1-1

A reaction vessel (9-phenyl -9 H - carbazol-3-yl) boronic acid (30g, 104.49 mmol), 1- bromo-4-iodo-benzene (30g, 104.49 mmol), tetrakis (triphenyl Palladium (3.6 g, 3.13 mmol), sodium carbonate (28 g, 261.23 mmol), toluene (520 mL) and ethanol (130 mL) were added to the reaction mixture. 130 mL of distilled water was added and the mixture was stirred at 120 ° C for 4 hours. After the reaction was completed, the reaction mixture was washed with distilled water and extracted with ethyl acetate. The organic layer was dried over magnesium sulfate, and the solvent was removed by a rotary evaporator, and then purified by column chromatography to obtain Compound 1-1 (27 g, yield 65%).

Preparation of Compound 1-2

A reaction vessel Compound 1-1 (13g, 32.65 mmol), 3- (4,4,5,5- tetramethyl-1,3,2-dioxa-boran-2-yl) -9 H - carbazole (10 g, 39.18 mmol), tetrakis (triphenylphosphine) palladium (1.1 g, 0.98 mmol), potassium carbonate (11 g, 81.63 mmol), 160 mL of toluene, and 40 mL of ethanol were placed, 40 mL of distilled water was added, Lt; / RTI > for 4 hours. After the reaction was completed, the reaction mixture was washed with distilled water and extracted with ethyl acetate. The organic layer was dried over magnesium sulfate, and the solvent was removed by a rotary evaporator. The residue was purified by column chromatography to obtain Compound 1-2 (11 g, yield: 70%).

Preparation of Compound C-8

To the reaction vessel, Compound 1-2 (9.3 g, 19.26 mmol), (3-bromophenyl) triphenylsilane (12 g, 28.89 mmol), copper iodide (1.8 g, 9.63 mmol), ethylenediamine mL, 19.26 mmol), potassium phosphate (10 g, 48.15 mmol), and toluene (100 mL) were added, followed by stirring at 120 ° C for 4 hours. After the reaction was completed, the reaction mixture was washed with distilled water and extracted with ethyl acetate. The organic layer was dried over magnesium sulfate, and the solvent was removed using a rotary evaporator. The residue was purified by column chromatography to obtain Compound C-8 (10 g, yield 64%).

 [ Example  2] Preparation of Compound C-2

Preparation of Compound C-2

To the reaction vessel 9-phenyl -9 H, 9 'H -3,3'- non carbazole (8g, 19.58 mmol), ( 3- bromo-phenyl) triphenyl silane (9.8 g, 23.50 mmol), tris (di (0.9 g, 1.00 mmol), tri-t-butylphosphine (0.9 mL, 1.96 mmol), sodium tert-butoxide (2.8 g, 29.37 mmol) and 100 mL of toluene were added And the mixture was stirred at 120 ° C for 4 hours. After the reaction was completed, the reaction mixture was washed with distilled water and extracted with ethyl acetate. The organic layer was dried over magnesium sulfate, and the solvent was removed using a rotary evaporator, followed by purification by column chromatography to obtain Compound C-2 (2.7 g, yield: 19%).

[ Example  3] Preparation of Compound C-4

Preparation of Compound C-4

To a flask was added 9 - (- 3-bromophenyl) -9'phenyl-3,3'bis-9H-carbazole (12 g, 31.8 mmol), B- [3- (triphenylsilyl) phenyl] 12g, 31.8mmol), tetrakis (triphenylphosphine) palladium _{(O) (Pd (PPh 3} ) 4) (1.0g, 0.88mmol), 2M K 2 CO 3 (6.1g, 44.3mmol), toluene 100 mL And 25 mL of ethanol were added to dissolve and refluxed for 4 hours. After the reaction was completed, the organic layer was extracted with ethyl acetate, and the residue was dried over magnesium sulfate. The organic layer was dried and separated by column chromatography to obtain Compound C-4 (9.5 g, yield 69%).

[device Example  1] Using the organic electronic material compound of the present invention OLED  Device fabrication

An OLED device having a structure using the light emitting material of the present invention was fabricated. First, a transparent electrode ITO thin film (10? /?) Obtained from a glass for OLED (manufactured by Geomatec) was subjected to ultrasonic cleaning using acetone and isopropanol in succession, and then stored in isopropanol for storage. Next, an ITO substrate was mounted on a substrate holder of a vacuum deposition apparatus, and N4, N4'-biphenyl-N4, N4'-bis (9-phenyl-9H-carbazol- - [1,1'-biphenyl] -4,4'-diamine was introduced into the chamber and evacuated until the degree of vacuum in the chamber reached 10E-6 torr. Then, current was applied to the cell to evaporate, A hole injection layer was deposited. Subsequently, 1,4,5,8,9,11-hexaazatriphenylene-hexacarbonitrile (HAT-CN) was placed in another cell in the vacuum vapor deposition apparatus, and a current was applied to the cell to evaporate it to form a hole injection layer 1 A hole injection layer 2 with a thickness of 5 nm was deposited. Subsequently, Compound T-1 shown in [Table 1] below was placed in another cell in a vacuum deposition apparatus, and a current was applied to the cell to evaporate the hole transport layer 1 to deposit a hole transport layer 1 having a thickness of 10 nm on the hole injection layer 2. Subsequently, a compound C-2 was added to another cell in a vacuum vapor deposition apparatus, and a current was applied to the cell to evaporate it, thereby depositing a hole transporting layer 2 having a thickness of 30 nm on the hole transporting layer 1. A hole injecting layer and a hole transporting layer were formed, and then a light emitting layer was deposited thereon as follows. The compounds H-1 and H-2 shown in [Table 1] were added to two cells in a vacuum deposition apparatus, and the compound D-25 was added as a dopant to another cell. 1, and at the same time, the dopant material is vaporized at different rates to form a 40 nm thick light emitting layer on the second hole transport layer by doping the dopant in an amount of 5% by weight with respect to the total amount of the host and the dopant Respectively. Then, on one side of the luminescent layer, an electron transport layer was formed by adding a solution of 2- (4- (9,10-di (naphthalen-2-yl) anthracen- And lithium quinolate was added to another cell. Then, the two materials were evaporated at the same rate and doped with 50% by weight to deposit an electron transport layer of 35 nm. Then, lithium quinolate was deposited to a thickness of 2 nm as an electron injecting layer, and then an Al cathode was deposited to a thickness of 80 nm using another vacuum vapor deposition apparatus to fabricate an OLED device. Each compound was purified by vacuum sublimation under 10 ^-6 torr.

As a result, a current of 2.3 mA / cm < ² > flowed and green luminescence of 1500 cd / m < ² > was confirmed. At a constant current of 15,000 nits brightness, 220 hours were confirmed as a result of the time to reach 85% of the initial luminance.

[device Example  2] Using the light emitting material of the present invention OLED  Device fabrication

An OLED device was fabricated in the same manner as in Example 1, except that Compound C-4 was deposited to a thickness of 30 nm as the hole transport layer 2.

As a result, a current of 3.1 mA / cm < ² > flowed and green light emission of 2000 cd / m < ² > was confirmed. At a constant current of 15,000 nits brightness, 200 hours were confirmed as a result of the time to reach 85% of the initial luminance.

[device Comparative Example  1] Using conventional light emitting materials OLED  Device fabrication

An OLED device was fabricated in the same manner as in Example 1 except that the compound T-1 shown in [Table 1] below was deposited as the hole transport layer 2 to a thickness of 30 nm.

As a result, a current of 14.8 mA / cm < ² > flowed, and green emission of 5000 cd / m < ² > was confirmed. 150,000 nits As a result of the lifetime of reaching 85% of the initial luminance at a constant current based on luminance, 150 hours was confirmed.

[device Comparative Example  2] Using a conventional light emitting material OLED  Device fabrication

An OLED device was fabricated in the same manner as in Example 1, except that Compound B-1 shown in [Table 1] below was deposited as a hole transport layer 2 to a thickness of 30 nm.

As a result, a current of 12.8 mA / cm < ² > flowed and a green luminescence of 6000 cd / m < ² > was confirmed. One hour was confirmed as a result of the lifetime of reaching 85% of the initial luminance at a constant current of 15,000 nits brightness.

It was confirmed that the luminescent properties of the compounds for organic electronic materials developed in the present invention exhibit excellent characteristics compared to the conventional materials. Further, the device using the compound for organic electronic material according to the present invention has excellent luminescence characteristics and good lifetime characteristics.

Claims (9)

An organic electroluminescent compound represented by the following Formula 1:
[Chemical Formula 1]

In Formula 1,
Ar ₁ is substituted or unsubstituted nitrogen (N) (5-30 membered) heteroaryl, or substituted or unsubstituted (C 6 -C 30) aryl;
Ar ₂ And Ar ₃ are each independently substituted or unsubstituted (5-30 membered) heteroaryl, or substituted or unsubstituted (C6-C30) aryl;
L ₁ is a single bond, substituted or unsubstituted (C6-C30) arylene, or substituted or unsubstituted (3-30 membered) heteroarylene;
R ₁ to R ₄ are each independently hydrogen, deuterium, halogen, cyano, carboxyl, nitro, hydroxy, substituted or unsubstituted (C 1 -C 30) alkyl, substituted or unsubstituted (C 3 -C 30) , Substituted or unsubstituted (C3-C30) cycloalkenyl, substituted or unsubstituted (3-7 membered) heterocycloalkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (3- 30 membered) heteroaryl, a substituted or unsubstituted mono (C6-C30) arylamino, a substituted or unsubstituted mono- (C1-C30) alkylamino, -NR ₅ R ₆ or or -SiR ₇ R ₈ R _9, adjacent (C3-C30) monocyclic or polycyclic alicyclic or aromatic ring optionally substituted with a substituent;
R ₅ to R ₉ are each independently substituted or unsubstituted (C 1 -C 30) alkyl, substituted or unsubstituted (C 6 -C 30) aryl, or substituted or unsubstituted (3-30 membered) heteroaryl;
The carbon atom of the alicyclic or aromatic ring may be replaced by one or more heteroatoms selected from nitrogen, oxygen and sulfur;
Wherein said heteroaryl and said heterocycloalkyl comprise at least one heteroatom selected from B, N, O, S, P (= O), Si and P;
a and d are each independently an integer of 1 to 4; When a or d is an integer of 2 or more, each R ₁ or R ₄ may be the same or different;
b and c are each independently an integer of 1 to 3; When b or c is an integer of 2 or more, each R ₂ or R ₃ may be the same or different. The organic electroluminescent compound according to claim 1, wherein the compound of formula (1) is represented by any one of the following formulas (2) to (5).
[Chemical Formula 2] < EMI ID =

[Chemical Formula 4]

In the above formulas 2 to 5,
Ar ₁ to Ar ₃ , L ₁ , and R ₁ to R ₄ are as defined in claim 1. _2. The compound of claim 1, wherein Ar < 1 > is substituted or unsubstituted (C6-C30) aryl; Wherein Ar ₂ and Ar ₃ are each independently substituted or unsubstituted (5-20 membered) heteroaryl or substituted or unsubstituted (C 6 -C 20) aryl; Said L < _{1 >} is a single bond, substituted or unsubstituted (C6-C20) arylene, or substituted or unsubstituted (5-20 membered) heteroarylene; Wherein R ₁ to R ₄ are each independently selected from the group consisting of hydrogen, substituted or unsubstituted (C 1 -C 20) alkyl, substituted or unsubstituted (C 5 -C 20) cycloalkyl, substituted or unsubstituted (3-7 membered) (C3-C20) monocyclic or polycyclic (C1-C20) alkyl, substituted or unsubstituted aryl, or substituted or unsubstituted (5-20 membered heteroaryl) An alicyclic group or an aromatic ring. The compound according to claim 1, wherein Ar ₁ is substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted terphenyl, substituted or unsubstituted anthracenyl, substituted Substituted or unsubstituted phenanthrenyl, substituted or unsubstituted tetracenyl, substituted or unsubstituted triphenylenyl, substituted or unsubstituted creicenyl, substituted or unsubstituted pyrenyl, substituted or unsubstituted phenylnaphthyl, Substituted or unsubstituted naphthylphenyl, substituted or unsubstituted fluorenyl, or substituted or unsubstituted spirobifluorenyl. The compound according to claim 1, wherein Ar ₂ is substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted terphenyl, substituted or unsubstituted anthracenyl, substituted Substituted or unsubstituted phenanthrenyl, substituted or unsubstituted tetracenyl, substituted or unsubstituted triphenylenyl, substituted or unsubstituted creicenyl, substituted or unsubstituted pyrenyl, substituted or unsubstituted phenylnaphthyl, Substituted or unsubstituted naphthylphenyl, or substituted or unsubstituted fluorenyl. The organic electroluminescent compound according to claim 1, wherein Ar ₃ is substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, or substituted or unsubstituted naphthyl. The compound according to claim 1, wherein L < ₁ > is substituted or unsubstituted phenylene, substituted or unsubstituted biphenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted terphenylene, substituted or unsubstituted anthra Substituted or unsubstituted phenanthrenylene, substituted or unsubstituted tetracenylene, substituted or unsubstituted triphenylenylene, substituted or unsubstituted pyrenylene, substituted or unsubstituted pyrenylene, substituted or unsubstituted pyrenylene, substituted or unsubstituted pyrenylene, An unsubstituted phenylnaphthylene, a substituted or unsubstituted naphthylphenylene, or a substituted or unsubstituted fluorenylene. The organic electroluminescent compound according to claim 1, wherein the compound of Formula 1 is selected from the following compounds.

An organic electroluminescent device comprising the compound of claim 1.