TW201420582A - A novel organic electroluminescence compound and an organic electroluminescence device containing the same - Google Patents

Abstract

The present invention relates to a novel organic electroluminescent compound and an organic electroluminescent device comprising the same. The organic electroluminescent compound according to the present invention has superior luminous efficiency, and can provide an organic electroluminescent device having improved power efficiency by reducing the driving voltage of the device.

Description

Novel organic electroluminescent compound and organic electric field illuminating device containing the same

The present invention relates to a novel organic electroluminescent compound and an organic electric field illuminating device comprising the same.

An electric field illuminating (EL) device is a self-illuminating device that has the following advantages over other display devices because it provides a wider viewing angle, a larger contrast ratio, and a faster reaction time. The organic EL device was first developed by Eastman Kodak by using an aromatic diamine small molecule and an aluminum complex as a material to form a light-emitting layer [Appl. Phys. Lett. 51, 913, 1987].

The most important factor determining the luminous efficiency of an organic EL device is a luminescent material. Fluorescent materials have been widely used as luminescent materials so far. However, in view of the electric field illuminating mechanism, since the phosphorescent luminescent material theoretically increases the luminous efficiency by 4 times compared with the fluorescent luminescent material, the research and development of the phosphorescent luminescent material has been extensively studied. In this view, the ruthenium (III) complex is a widely known phosphorescent material comprising bis(2-(2'-benzothienyl)-pyridine-N,C-3') oxime (ethinylacetone). )[(acac)Ir(btp) ₂ ], ginseng (2-phenylpyridine) hydrazine [Ir(ppy) ₃ ] and bis(4,6-difluorophenylpyridine-N,C2)pyridinecarboxamide [ Firpic is used as red, green and blue light, respectively.

In order to improve color purity, luminous efficiency, and stability, a host material in which a light-emitting material (dopant) is mixed may be used as the light-emitting material. Since the host material has a large influence on the efficiency and performance of the light-emitting device, it is important to select the host material when using such a light-emitting material (dopant)/host material system. In general, 4,4'-N,N'-dicarbazole-biphenyl (CBP) is the most widely known phosphorescent host material. In recent years, Pioneer (Japan) has developed a high-performance organic EL device using Bathocuproine (BCP) and bis(2-methyl-8-hydroxyquinolinyl) as a blocking material for holes. 4-phenylphenol) aluminum (III) (BAlq) or the like is used as a host material.

While these phosphorescent host materials have certain advantages in view of luminescent properties, such materials have the following disadvantages: (1) high temperature deposition of such materials in vacuum due to the low glass transition temperature and poor thermal stability of the materials. May degrade during the process. (2) The power efficiency of the organic EL device is determined by [(π/voltage) × current efficiency], and the power efficiency is inversely proportional to the voltage. Organic EL devices including phosphorescent host materials provide higher current efficiency (cd/A) than those comprising phosphor materials. However, it has a higher driving voltage and, therefore, does not have substantial advantages in terms of power efficiency (lm/W). (3) Furthermore, when the phosphorescent host material is used in an OLED device, the operational life of the device is not satisfactory, and the luminous efficiency still needs to be improved.

At the same time, copper phthalocyanine (CuPc), 4,4'-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (NPB), N,N'-diphenyl- N,N'-bis(3-methylphenyl)-(1,1'-biphenyl)-4,4'-diamine (TPD), 4,4',4"-para (3-methyl Phenylphenylamino)triphenylamine (MTDATA) is used as a hole injection and transport material in an organic EL device. However, such a material has a reduced quantum efficiency and lifetime of an organic EL device. The problem is that when the organic EL device is operated at a high current, thermal stress occurs between the anode and the hole injection material layer, and is lowered. The life of the device. Furthermore, since the organic material used for the hole injection layer has high hole mobility, the hole-electron charge balance is lost and the quantum efficiency (cd/A) is lowered.

The carbazole-containing amine compound used in an organic electric field light-emitting device is disclosed in Korean Patent Application Publication No. 2009-0035729A. Further, Korean Patent Application Publication No. 2011-0129766A discloses a fused carbazole-containing amine compound for use in an organic electric field light-emitting device. However, the power efficiency, luminous efficiency, quantum efficiency, and lifetime of organic EL devices including such compounds disclosed in these documents are still unsatisfactory.

SUMMARY OF THE INVENTION An object of the present invention is to provide an organic electric field luminescent compound which has high luminous efficiency and good lifetime compared to conventional materials, and an organic electric field illuminating device having high efficiency and long life.

The inventors have found that the above object can be achieved by a compound represented by the following formula 1:

Wherein, L ₁ and L ₂ each independently represent a single bond, a substituted or unsubstituted (C6-C30) extended aryl group, or a substituted or unsubstituted 5 to 30 membered heteroaryl group; Ar ₁ and Ar ₂ each independently represents a substituted or unsubstituted (C6-C30) aryl group, or a substituted or unsubstituted 5 to 30 membered heteroaryl group; X represents an oxygen atom, a sulfur atom, or -CR ₅ R ₆ -; R ₁ to R ₆ each independently represent hydrogen, deuterium, halogen, cyano, carboxy, nitro, hydroxy, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted ( C2-C30) alkenyl, substituted or unsubstituted (C2-C30) alkynyl, substituted or unsubstituted (C1-C30) alkoxy, substituted or unsubstituted (C3-C30) Cycloalkyl, substituted or unsubstituted (C3-C30)cycloalkenyl, substituted or unsubstituted 3 to 7 membered heterocycloalkyl, substituted or unsubstituted (C6-C30) aryl a (C6-C30) aryl group fused to a (C3-C30)cycloalkyl group, or a substituted or unsubstituted 5 to 30 membered heteroaryl group, -NR ₁₁ R ₁₂ , -SiR ₁₃ R _{14 R 15, -SR 16, -OR 17} , -COR 18 , or _{-B (oR 19) (oR 20} ); or the R ₁ to R ₆ taken with the adjacent Group is attached form a monocyclic or polycyclic 3 to 30 of the alicyclic or aromatic ring carbon atom of the ring may be at least one hetero atom selected from nitrogen, oxygen and sulfur of substituted; R ₁₁ to R ₂₀ are each independently Represents hydrogen, deuterium, halogen, cyano, carboxy, nitro, hydroxy, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C2-C30) alkenyl, substituted or Unsubstituted (C2-C30) alkynyl, substituted or unsubstituted (C1-C30) alkoxy, substituted or unsubstituted (C3-C30) cycloalkyl, substituted or unsubstituted (C3-C30)cycloalkenyl, substituted or unsubstituted 3 to 7 membered heterocycloalkyl, substituted or unsubstituted (C6-C30) aryl, or substituted or unsubstituted 5 to 30 membered heteroaryl; or the R ₁₁ to R _{20 are} bonded to an adjacent substituent to form a monocyclic or polycyclic 3 to 30 membered alicyclic or aromatic ring, the ring having at least carbon atoms a hetero atom substitution selected from the group consisting of nitrogen, oxygen and sulfur; a represents an integer from 1 to 4; when a is an integer of 2 or more, each R ₁ is the same or different; b to d each independently represent an integer from 1 to 3; When b, c or d is an integer of 2 or more, R _2, each R _3, the same or different and each R ₄ system; the (stretch) heteroaryl containing at least one selected from B, N, O, S, P (= O), Si, and P the heteroatom; and The heterocycloalkyl group contains at least one hetero atom selected from the group consisting of O, S and N.

The organic electroluminescent compound of the present invention has material properties of high luminous efficiency and good lifetime, and thus can provide an organic electric field light-emitting device having an excellent operational life. Furthermore, the organic electroluminescent compound of the present invention can simultaneously reduce the driving voltage of the organic electric field light-emitting device and improve the power efficiency.

The invention is described in detail below. The following description is intended to be illustrative of the invention and is not intended to limit the scope of the invention in any way.

The present invention relates to an organic electroluminescent compound of the above formula 1, an organic electroluminescent material comprising the compound, and an organic electric field light-emitting device comprising the same.

The organic electroluminescent compound shown in the above formula 1 will be described in detail below.

In Formula 1, L ₁ and L ₂ each independently represent a single bond, a substituted or unsubstituted (C6-C30) extended aryl group, or a substituted or unsubstituted 5 to 30 membered heteroaryl group; Preferably, it is a single bond, a substituted or unsubstituted (C6-C20) extended aryl group, or a substituted or unsubstituted 5 to 15 member heteroaryl; more preferably a single bond, unsubstituted or via (C1-C6)alkyl, (C1-C15)aryl or di(C6-C15)arylamino substituted (C6-C20) extended aryl, or unsubstituted 5 to 10 members base.

In the above formula 1, Ar ₁ and Ar ₂ each independently represent a substituted or unsubstituted (C6-C30) aryl group, or a substituted or unsubstituted 5 to 30 membered heteroaryl group; preferably substituted Or unsubstituted (C6-C15) aryl, or substituted or unsubstituted 5 to 15 membered heteroaryl; more preferably unsubstituted or substituted (C1-C6) alkyl, (C6-C15 An aryl, di(C6-C15)arylamino group, or (C6-C15)aryl (5 to 10 membered) heteroarylamino substituted (C6-C15) aryl, or unsubstituted or 5- to 10-membered heteroaryl substituted with (C6-C15) aryl or di(C6-C15) arylamine.

In the above formula 1, X represents an oxygen atom, a sulfur atom, or -CR ₅ R ₆ -.

In the above formula 1, R ₁ to R ₆ each independently represent hydrogen, deuterium, halogen, cyano, carboxyl, nitro, hydroxy, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C2-C30)alkenyl, substituted or unsubstituted (C2-C30) alkynyl, substituted or unsubstituted (C1-C30) alkoxy, substituted or unsubstituted (C3- C30) cycloalkyl, substituted or unsubstituted (C3-C30) cycloalkenyl, substituted or unsubstituted 3 to 7 membered heterocycloalkyl, substituted or unsubstituted (C6-C30) Aryl, (C6-C30) aryl fused to (C3-C30)cycloalkyl, or substituted or unsubstituted 5 to 30 membered heteroaryl, -NR ₁₁ R ₁₂ , -SiR ₁₃ R ₁₄ R ₁₅ , -SR ₁₆ , -OR ₁₇ , -COR ₁₈ or -B(OR ₁₉ )(OR ₂₀ ); or the R ₁ to R _{6 are} bonded to an adjacent substituent to form a monocyclic or polycyclic ring a 3- to 30-membered alicyclic or aromatic ring, the carbon atom of which may be substituted with at least one hetero atom selected from nitrogen, oxygen and sulfur; preferably hydrogen, halogen, substituted or unsubstituted (C1- C15) alkyl, substituted or unsubstituted (C6-C15) aryl, (C6-C15) aryl fused to (C3-C20)cycloalkyl, taken Or non-substituted 5-15 heteroaryl, -NR ₁₁ R _12, or -SiR ₁₃ R ₁₄ R _15; more preferably hydrogen, halo, non-substituted (C1-C6) alkyl, without (C6-C15) aryl substituted with (C1-C6)alkyl or (C6-C15) aryl, (C6-C15) aryl fused to (C3-C7)cycloalkyl, unsubstituted Substituted 5 to 15 membered heteroaryl, or -NR ₁₁ R ₁₂ ; R ₁₁ to R ₂₀ preferably each independently represent substituted or unsubstituted (C6-C15) aryl, substituted or unsubstituted a 5- to 15-membered heteroaryl group; more preferably an unsubstituted (C6-C15) aryl group; and R ₁₃ to R ₁₅ each independently represent a substituted or unsubstituted (C1-C10) alkyl group, or Substituted or unsubstituted (C6-C15) aryl.

In one embodiment of the above formula 1 of the present invention, L ₁ and L ₂ each independently represent a single bond, a substituted or unsubstituted (C6-C20) extended aryl group, or a substituted or unsubstituted 5 member to 15 members are heteroaryl; Ar ₁ and Ar ₂ each independently represent a substituted or unsubstituted (C6-C15) aryl group, or a substituted or unsubstituted 5 to 15 membered heteroaryl; R ₁ to R ₆ each independently represents hydrogen, halogen, substituted or unsubstituted (C1-C15) alkyl, substituted or unsubstituted (C6-C15) aryl, fused to (C3-C20)cycloalkyl (C6-C15) aryl, or substituted or unsubstituted 5 to 15 membered heteroaryl, -NR ₁₁ R ₁₂ or -SiR ₁₃ R ₁₄ R ₁₅ ; wherein R ₁₁ and R ₁₂ are each independently represented Substituted or unsubstituted (C6-C15) aryl, or substituted or unsubstituted 5 to 15 membered heteroaryl; and R ₁₃ to R ₁₅ each independently represent substituted or unsubstituted (C1 -C10)alkyl, or substituted or unsubstituted (C6-C15) aryl.

In another embodiment of Formula 1 above, L ₁ and L ₂ each independently represent a single bond, unsubstituted or via (C1-C6)alkyl, (C6-C15)aryl, or di(C6- C15) an arylamino group-substituted (C6-C20) extended aryl group, or an unsubstituted 5 to 10 membered heteroaryl group; Ar ₁ and Ar ₂ each independently represent unsubstituted or via (C1-C6) Alkyl, (C6-C15) aryl, di(C6-C15)arylamino, or (C6-C15)aryl (5 to 10 membered) heteroarylamine substituted (C6-C15) aryl a 5- to 10-membered heteroaryl group which is unsubstituted or substituted with a (C6-C15) aryl group or a di(C6-C15) arylamine group; and R ₁ to R ₆ each independently represent hydrogen, halogen, or Substituted (C1-C6)alkyl, unsubstituted or substituted by (C1-C6)alkyl or (C6-C15)aryl (C6-C15) aryl, and (C3-C7)cycloalkyl a fused (C6-C15) aryl group, an unsubstituted 5 to 15 membered heteroaryl group, or -NR ₁₁ R ₁₂ ; wherein R ₁₁ and R ₁₂ each independently represent unsubstituted (C6-C15) Aryl.

As used herein, "(C1-C30)alkyl" means a straight or branched alkyl group having 1 to 30 carbon atoms, wherein the number of carbon atoms is preferably from 1 to 15, more preferably from 1 to 6. And including methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert-butyl; etc.; "(C2-C30)alkenyl" means having 2 to 30 carbon atoms a linear or branched alkenyl group having preferably 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, and containing a vinyl group, a 1-propenyl group, a 2-propenyl group, a 1-butenyl group, 2-butenyl, 3-butenyl and 2-methylbut-2-enyl, etc.; "(C2-C30)alkynyl" means a straight or branched alkynyl group having 2 to 30 carbon atoms Wherein the number of carbon atoms is preferably from 2 to 20, more preferably from 2 to 10, and includes an ethynyl group, a 1-propynyl group, a 2-propynyl group, a 1-butynyl group, a 2-butynyl group, 3-butynyl, 1-methylpent-2-ynyl, etc.; "(C3-C30)cycloalkyl" is a monocyclic or polycyclic hydrocarbon having 3 to 30 carbon atoms, wherein the number of carbon atoms is preferably It is 3 to 20, more preferably 3 to 7, and contains a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, etc.; the "3 to 7 membered heterocycloalkyl group" has at least one a cycloalkyl group derived from a hetero atom of B, N, O, S, P(=O), Si and P, preferably O, S and N, and 3 to 7 ring skeleton atoms, and comprising tetrahydrofuran, pyrrolidine , (tetrahydrothiophene, tetrahydropyran, etc.; "(C6-C30) (extended) aryl" is a monocyclic or fused ring derived from an aromatic hydrocarbon having 6 to 30 carbon atoms, wherein the number of carbon atoms is preferably It is 6 to 20, more preferably 6 to 15, and contains a phenyl group, a biphenyl group, a triphenylene group, a naphthyl group, an anthryl group, a phenanthryl group, an anthracenyl group, a fluorenyl group, and a triphenylenyl group. , fluorenyl, tetracenyl, sulfhydryl, chrysenyl, naphthacenyl, fluoranthenyl, etc.; "5 to 30 members (extension) "Aryl" is a hetero atom having at least one, preferably 1 to 4 groups selected from the group consisting of B, N, O, S, P(=O), Si and P, and 5 to 30 ring skeleton atoms An aryl group; a fused ring which is monocyclic or condensed with at least one benzene ring, preferably has 5 to 15, more preferably 5 to 10 ring skeleton atoms, may be partially saturated, and may be a single bond and at least a heteroaryl or aryl heteroaryl group, and includes a monocyclic type An aryl group, comprising a line furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, iso Azolyl, Azolyl, Diazolyl, three Base, four Base, triazolyl, tetrazolyl, furazolyl, pyridyl, pyridyl Base, pyrimidinyl, oxime And the fused cycloheteroaryl group, including benzofuranyl, benzothienyl, isobenzofuranyl, dibenzofuranyl, dibenzothiophenyl, benzimidazolyl, benzothiazole Benzoisothiazolyl, benzopyrene Azolyl, benzo Azyl, isodecyl, fluorenyl, oxazolyl, benzothiadiazolyl, quinolinyl, isoquinolyl, cinnolinyl, quinazolinyl, quin Orolinyl, carbazolyl, brown A phenyl, benzodioxolyl or the like. Further, "halogen" includes F, Cl, Br, and I.

As used herein, the expression "substituted" in "substituted or unsubstituted" means that a hydrogen atom in a functional group is replaced by another atom or group (ie, a substituent). In the above formula 1, a substituted (C1-C30) alkyl group, a substituted (C2-C30) alkenyl group, a substituted (C2-C30) alkynyl group, a substituted (C1-C30) alkoxy group, Substituted (C3-C30)cycloalkyl, substituted (C3-C30)cycloalkyl, substituted 3 to 7 heterocycloalkyl, substituted (C6-C30) (extended) aryl Or substituted 5 to 30 member(extension) heteroaryl substituents each independently are at least one selected from the group consisting of hydrazine, halogen, cyano, carboxyl, nitro, hydroxy, ( C1-C30)alkyl, halo(C1-C30)alkyl, (C2-C30)alkenyl, (C2-C30)alkynyl, (C1-C30)alkoxy, (C1-C30) Alkylthio, (C3-C30)cycloalkyl, (C3-C30)cycloalkenyl, 3- to 7-membered heterocycloalkyl, (C6-C30)aryloxy, (C6-C30)aryl (C6-C30) aryl, unsubstituted or substituted with (C6-C30) aryl, 5- to 30-membered heteroaryl, unsubstituted or substituted by 5 to 30 membered heteroaryl, 3 (C1-C30)alkyldecylalkyl, tris(C6-C30)aryldecylalkyl, di(C1-C30)alkyl(C6-C30)aryldecylalkyl, (C1-C30)alkyldi(C6- C30) aryl decyl, amino, mono or di(C1-C30)alkylamino, mono or di(C6-C30) arylamino, (C1-C30)alkyl (C6-C30) aryl Amino, (C1-C30)alkylcarbonyl, (C1-C30)alkoxycarbonyl, (C6-C30)arylcarbonyl, di(C6-C30)arylboryl, di(C1-C30)alkyl Boron, (C1-C30)alkyl (C6-C30) aryl boron, (C6-C30) aryl (C1-C30) alkyl, and (C1-C30) alkyl (C6-C30) aryl Preferably, each is independently at least one member selected from the group consisting of: (C1-C6)alkyl, (C6-C15)aryl, di(C6-C15)arylamine, and (C6) -C15) aryl (5 to 10 members) heteroarylamino group.

Representative organic electroluminescent compounds of the invention comprise the following compounds:

The organic electroluminescent compound of the present invention can be prepared according to conventional reactions in the art to which the invention pertains, for example, the following reaction scheme:

Here, X, L ₁ , L ₂ , Ar ₁ , Ar ₂ , R ₁ to R ₄ , a, b, c and d in the reaction scheme 1 are as defined in the above formula 1, and Hal represents a halogen atom.

The reaction of Reaction Scheme 1 is carried out in an aromatic hydrocarbon or a general polar organic solvent (for example, benzene, toluene, xylene, tetrahydrofuran, two Under alkane, or a combination of these, it is preferably toluene. Further, the reaction is carried out in an alkali metal hydroxide or carbonate (for example, NaOH, KOH, Na ₂ CO ₃ , K ₂ CO ₃ , Cs ₂ CO _{3 ,} etc.), preferably an aqueous K ₂ CO ₃ solution.

In general, the reaction temperature is selected from the range of from 40 to 180 ° C under reflux, and the reaction time is selected from the range of from 1 to 80 hours, preferably from 2 to 24 hours.

According to a preferred embodiment of the present invention, a catalyst mainly composed of Pt, particularly (Ph ₃ P) ₄ Pd or a derivative thereof, is a general catalyst used in the reaction to carry out a coupling reaction or a polycondensation reaction. The catalyst is added in the form of a solution or suspension.

Further, the compound of the present invention obtained in the reaction can be isolated by a method known in the art to which the invention pertains. For example, ethyl acetate (EA) / H ₂ O The reaction mixture was extracted, and dried MgSO _4. The resulting product is then distilled under reduced pressure and separated by column chromatography to give the compound of the invention.

The present invention provides an organic electroluminescent material comprising an organic electroluminescent compound of Formula 1, and an organic electric field illuminating device comprising the same.

The above materials may be composed solely of the organic electroluminescent compound of the present invention, or may comprise a conventional material usually contained in an organic electroluminescent material.

The organic electric field light-emitting device includes a first electrode, a second electrode, and at least one organic layer between the first and second electrodes. The organic layer may include at least one organic electroluminescent compound of the formula 1 of the present invention.

One of the first and second electrodes is an anode and the other is a cathode. The organic layer includes a light emitting layer, and at least one layer is selected from the group consisting of a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, an intermediate layer, a hole blocking layer, and an electron blocking layer.

The organic electroluminescent compound of the formula 1 of the present invention may be composed of at least one of a light-emitting layer and a hole transport layer. When used in a hole transport layer, the compound of the formula 1 of the present invention may be included as a hole transport material. When used in the light-emitting layer, the compound of the formula 1 of the present invention may be included as a host material; preferably, the light-emitting layer may further comprise at least one dopant, and if necessary, may include the formula 1 of the present invention. Another compound other than the organic electric field luminescent compound serves as the second host material.

The second host material can be any known phosphorescent host. specifically, In view of luminous efficiency, a phosphorescent host selected from the group consisting of compounds selected from the following formulae 2 to 4 is particularly preferred.

H-(Cz-L ₄ ) _h -M----------(2)

H-(Cz) _i -L ₄ -M----------(3)

Among them, Cz represents the following structure:

R ₂₁ to R ₂₄ each independently represent hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted 5 to 30 membered heteroaryl, or R ₂₅ R ₂₆ R ₂₇ Si-; R ₂₅ to R ₂₇ each independently represent substituted or unsubstituted (C1-C30) alkyl, or substituted or unsubstituted (C6-C30) aryl; L ₄ represents a single bond, a substituted or unsubstituted (C6-C30) extended aryl group, or a substituted or unsubstituted 5 to 30 membered heteroaryl; M Represents a substituted or unsubstituted (C6-C30) aryl group, or a substituted or unsubstituted 5 to 30 membered heteroaryl group; Y ₁ and Y ₂ each independently represent -O-, -S-, - N(R ₃₁ )- or -C(R ₃₂ )(R ₃₃ )-, the restriction condition is that Y ₁ and Y _{2 are} not present at the same time; R ₃₁ to R ₃₃ each independently represent substituted or unsubstituted (C1-C30) An alkyl group, a substituted or unsubstituted (C6-C30) aryl group, or a substituted or unsubstituted 5 to 30 membered heteroaryl group, and R ₃₂ and R ₃₃ are the same or different; h and i Each independently represents an integer from 1 to 3; j, k, l, and m each independently represent an integer from 0 to 4; and when h, i, j, k, l, or m is 2 The integers above, each of the (Cz-L _4), each (HCz), each of R _21, each R _22, same or different, each R ₂₃ or R ₂₄ lines each.

In particular, preferred examples of the second host material are as follows:

In accordance with the present invention, the dopant used to fabricate the organic electroluminescent device is preferably one or more phosphorescent dopants. The phosphorescent dopant material applied to the electric field light-emitting device of the present invention is not limited, but is preferably selected from the group consisting of complex compounds of iridium (Ir), osmium (Os), copper (Cu) and platinum (Pt); Preferably, it is an ortho-metalated complex compound of iridium (Ir), osmium (Os), copper (Cu), and platinum (Pt); and more preferably an ortho-metallated ruthenium complex compound.

According to the present invention, the phosphorescent dopant included in the organic electric field light-emitting device may be selected from the compounds represented by the following formulas 5 to 7.

Wherein L is selected from the following structures:

R ₁₀₀ represents hydrogen, or substituted or unsubstituted (C1-C30)alkyl; R ₁₀₁ to R ₁₀₉ , and R ₁₁₁ to R ₁₂₃ each independently represent hydrogen, deuterium, halogen, unsubstituted or substituted by halogen. (C1-C30) alkyl, cyano, substituted or unsubstituted (C1-C30) alkoxy, or substituted or unsubstituted (C3-C30) cycloalkyl; or the R ₁₂₀ to R _{123 is} bonded to an adjacent substituent to form a monocyclic or polycyclic 3- to 30-membered alicyclic or aromatic ring (eg, quinoline); R ₁₂₄ to R ₁₂₇ each independently represent hydrogen, deuterium, halogen, substituted or Unsubstituted (C1-C30) alkyl, or substituted or unsubstituted (C6-C30) aryl; wherein R ₁₂₄ to R ₁₂₇ are aryl, adjacent substituents may be substituted with adjacent The group is bonded to form a monocyclic or polycyclic ring of 3 to 30 members of an alicyclic or aromatic ring (for example, hydrazine); and R ₂₀₁ to R ₂₁₁ each independently represent hydrogen, deuterium, halogen, unsubstituted or substituted by halogen (C1) -C30)alkyl; f and g each independently represent an integer from 1 to 3; when f or g is an integer of 2 or more, each R ₁₀₀ is the same or different; and n is an integer from 1 to 3.

Specifically, the phosphorescent dopant may be selected from the compounds shown by the following compounds:

The present invention provides a material for an organic electric field illuminating device. The material includes a first host material and a second host material, wherein the compound of the present invention can be included as the first host material, wherein the ratio of the first host material to the second host material can range from 1:99 to 99:1 Within the scope.

Furthermore, the organic electric field light-emitting device includes a first electrode, a second electrode, and at least one organic layer interposed between the first and second electrodes. The organic layer includes a light emitting layer, wherein the light emitting layer includes an organic electric field light emitting device for use in the present invention The material and the material used as the host material for the organic electric field light-emitting device of the present invention.

The organic electroluminescence device of the present invention may further comprise at least one compound selected from the group consisting of an aromatic amine-based compound and a styryl aromatic amine-based compound in addition to the compound represented by Formula 1.

In the organic electroluminescence device of the present invention, the organic layer may further comprise at least one metal selected from the group consisting of metals of the first group of the periodic table, metals of the second group, transition metals of the fourth cycle, and a 5-period transition metal, an organometallic metal of a lanthanide metal and a d-transition element, or at least one complex compound including the metal. The organic layer may include a light emitting layer and a charge generating layer.

In addition, the organic electroluminescent device can emit white light by including at least one luminescent layer, which includes a blue electric field luminescent compound, a red electric field luminescent compound or a green electric field luminescent compound in addition to the compound of the present invention. In addition, the device includes a yellow or orange light emitting layer if necessary.

According to the present invention, at least one layer of the organic electroluminescent device (hereinafter referred to as "surface layer") is preferably selected from the group consisting of a chalcogenide layer, a metal halide layer and a metal oxide layer, which may be disposed on a single electrode or two On the inner surface of the electrodes. In particular, it is preferred to provide a chalcogenide (including oxide) layer of tantalum or aluminum on the anode surface of the electric field luminescent medium layer, and a metal halide layer or metal oxide layer on the cathode surface of the electric field luminescent medium layer. This surface layer provides operational stability of the organic electric field illuminating device. The chalcogen compound preferably comprises SiO _X (1 X 2), AlO _X (1 X 1.5), SiON, SiAlON, etc.; the metal halide preferably comprises LiF, MgF ₂ , CaF ₂ , a rare earth metal element fluoride, etc.; and the metal oxide preferably comprises Cs ₂ O, Li ₂ O, MgO, SrO, BaO, CaO and so on.

Preferably, in the organic electroluminescence device of the present invention, a mixed region of the electron transporting compound and the reducing dopant, or a mixed region of the hole transporting compound and the oxidizing dopant may be disposed on at least one surface of the electrode pair. . In this case, the electron transporting compound is reduced to an anion, and thus it becomes easier to inject or transport electrons from the mixed region to the electric field illuminating medium. Furthermore, the hole transport compound oxidizes to a cation, thus making it easier to inject or transport holes from the mixed region to the electric field illuminating medium. The oxidizing dopant preferably comprises a plurality of Lewis acids and acceptor compounds; and the reducing dopant preferably comprises an alkali metal, an alkali metal compound, an alkaline earth metal, a rare earth metal, and mixtures thereof. The reducing dopant layer can function as a charge generating layer to fabricate an electric field illuminating device having two or more layers of an electric field luminescent layer and emitting white light.

In order to form the respective layers of the organic electric field light-emitting device, according to the present invention, a dry film formation method such as vacuum evaporation, sputtering, plasma and ion plating, or wet film formation such as spin coating, dipping may be used. Coating method, and flow coating method.

When the wet film formation method is applied, the material forming the layers is dissolved or diffused in any suitable solvent (eg, ethanol, chloroform, tetrahydrofuran, two). Alkane, etc.) can form a film. Unless the solvent is problematic in film forming properties, the solvent can be any solvent that can dissolve or diffuse the materials.

Hereinafter, the representative organic electroluminescent compound of the present invention, the preparation method of the compound, and the luminescent properties of the device comprising the compound will be described in detail with reference to the following examples, but the invention is not limited to the following examples.

Example 1: Preparation of Compound C-80 Preparation of Compound 1-3

63 g (0.177 mol) of compound 1-1, 30 g (0.177 mol) of compound 1-2, 26 g (0.266 mol) of sodium butoxide (NaOt-Bu) and 4.3 g (0.014 mol) of tri(o-benzyl) After the phosphine (P(o-Tol) ₃ ) was dissolved in 1.7 L of toluene, 3.2 g (0.004 mol) of bis(dibenzylideneacetone)dipalladium(0) (Pd ₂ (dba) ₃ ) was added. The mixture was stirred at 120 ° C for 3 hours. The reaction was cooled to room temperature and extracted with 1 mL EtOAc. The resulting organic layer was washed with 400 mL of distilled water. The organic solvent was removed under reduced pressure. After filtration, the resulting solid was washed with methanol and dried. The obtained product was separated by hydrazine column chromatography and recrystallized to give compound 1-3, 41 g (58%).

Preparation of compound 1-4

After dissolving 10 g (25 mmol) of compound 1-3 in 150 mL of tetrahydrofuran (THF), 15 mL (37.50 mol) of n-BuLi (2.5 M in hexane) was added at -78 °C. The mixture was stirred at -78 ° C for 1 hour, and 4.2 mL (37.50 mol) of a trimethoxyborane (B(OMe) ₃ ) compound was added. All reactions were stirred for 2 hours, 100mL NH ₄ Cl and to terminate the reaction. After extracting with 200 mL of ethyl acetate, the obtained organic layer was washed with 100 mL of distilled water. The organic layer was dried with MgSO ₄ and the organic solvent was evaporated. The obtained solid was separated by recrystallization to give Compound 1-4, 5.4 g (59%).

Preparation of Compound 1-7

After dissolving 6.7 g (19.60 mmol) of compound 1-5, 4.1 g (17.82 mmol) of compound 1-6, and 4.7 g (44.55 mol) of Na ₂ CO ₃ in 90 mL of a toluene mixed solution, 20 mL of ethanol, 20 mL of distilled water, and 0.6 were added. g (0.53 mmol) of ruthenium (triphenylphosphine) palladium. The mixture was stirred at 120 ° C for 5 hours under reflux. The reaction was cooled to room temperature and extracted with EtOAc EtOAc. The resulting organic layer was washed with 100 mL of distilled water. The organic solvent was removed under reduced pressure. After filtration, the resulting solid was washed with methanol and dried. The obtained product was separated by hydrazine column chromatography and recrystallized to give compound 1-7, 3.7 g (47%).

Preparation of Compound C-80

After dissolving 3.7 g (8.30 mmol) of compound 1-7, 3.3 g (9.10 mmol) of compound 1-4 and 2.2 g (20.80 mmol) of Na ₂ CO ₃ in 44 mL of the mixed solution, 11 mL of ethanol and 11 mL of distilled water, 0.5 g ( 0.4 mmol) bismuth (triphenylphosphine) palladium. The mixture was stirred at 120 ° C for 5 hours under reflux. The reaction was cooled to room temperature and extracted with EtOAc EtOAc. The resulting organic layer was washed with 100 mL of distilled water. The organic solvent was removed under reduced pressure. After filtration, the resulting solid was washed with methanol and dried. The obtained product was separated by hydrazine column chromatography and recrystallized to give Compound C-80, 1.8 g (32%). MS/EIMS: found 685.90; calc.

Example 2: Preparation of Compound C-99

Preparation of compound 2-9

15 g (52 mmol) of 4-(diphenylamino)phenylboronic acid, 103.8 g (103.8 mmol) of 2,8-dibromobenzo[b,d]thiophene, 3 g (2.6 mmol) of ruthenium (triphenylphosphine) After palladium (0) [Pd(PPh ₃ ) ₄ ] and 14 g (130 mol) of Na ₂ CO _{3 were} placed in a round bottom flask, 250 mL of toluene, 50 mL of EtOH, and 50 mL of H ₂ O were added. The reaction mixture was stirred at 100 ° C for 2 hours. Ethyl acetate (EA) / H ₂ O and the reaction was extracted, dried in MgSO _4, and distilled under reduced pressure. The obtained product was separated by column chromatography to give compound 2-9, 13 g (58%).

Preparation of Compound C-99

6 g (13.9 mmol) of compound 2-9, 4 g (16.7 mmol) of 9,9-dimethyl-9H-indol-2-ylboronic acid, 0.8 g (0.7 mmol) of Pd(PPh ₃ ) ₄ and 4.8 g (35 mmol) K ₂ CO _{3 was} placed in a round bottom flask, and 45 mL of toluene, 15 mL of EtOH, and 15 mL of H ₂ O were added. The reaction mixture was stirred at 120 ° C for 2 hours. In EA / H ₂ O and the reaction was extracted, dried in MgSO _4, and distilled under reduced pressure. The obtained product was separated by column chromatography to yield Compound C-99, 3.9 g (45%).

MS/EIMS: found: 619.8; calc.

Apparatus Example 1: Manufacture of an OLED device using the compound of the present invention

The manufacture of an OLED device using the organic electroluminescent compound of the present invention is as follows.

First, an indium tin oxide (ITO) film (15 Ω/sq) for a transparent electrode on a glass substrate of an organic light emitting diode (OLED) device (Samsung Corning) is sequentially treated with trichloroethylene, acetone, ethanol, and The distilled water was washed with ultrasonic waves and then stored in isopropanol. Then, the ITO substrate was placed on a substrate holder of a vacuum vapor deposition apparatus. N ¹ ,N ¹ '-([1,1'-biphenyl]-4,4'-diyl)bis(N ¹ -(anthran-1-yl)-N ⁴ ,N ⁴ -diphenyl Benzyl-1,4-diamine) was introduced into one of the chambers of the vacuum vapor deposition apparatus, and then the chamber pressure of the apparatus was controlled to 10 ^-6 torr. Thereafter, a current was applied to the chamber to evaporate the introduced material, thereby forming a hole injection layer having a thickness of 60 nm on the ITO substrate. Then, the compound C-99 was introduced into another chamber of the vacuum vapor deposition apparatus, and an electric current was applied to the chamber to evaporate, thereby forming a hole transport layer having a thickness of 20 nm on the hole injection layer. After the hole injection layer and the hole transport layer are formed as described above, the light-emitting layer is deposited on the layers as described below.

5-(4-([1,1':4',1"-terphenyl)-3-yl)pyrimidin-2-yl)-5H-benzo[4,5]thieno[3,2 -c] oxazole is introduced into a chamber of a vacuum vapor deposition apparatus as a host material, and compound D-1 is introduced into another chamber as a dopant material, and the two materials are evaporated at different rates to doping of the deposition. The amount is 15% by weight based on the total amount of the host material and the dopant material to form a light-emitting layer having a thickness of 30 nm on the hole transport layer. Then, in order to form an electron transport layer on the formed light-emitting layer, Introducing 2-(4-(9,10-di(anthran-2-yl)indol-2-yl)phenyl)-1-phenyl-1H-benzo[d]imidazole into a small chamber and Lithium 8-hydroxyquinolate was introduced into another chamber, and the two materials were evaporated at the same rate to a deposition amount of 50% by weight, respectively. Thus, an electron transport layer having a thickness of 30 nm was formed on the light-emitting layer. In order to form an electron injecting layer, after depositing lithium hydroxyquinolate having a thickness of 2 nm, an Al cathode having a thickness of 150 nm is deposited by another vacuum vapor deposition apparatus. Thus, fabrication of the OLED device is completed. All materials Was used prior to the 10 ^-6 Torr was purified by vacuum sublimation.

Therefore, the manufactured OLED device exhibited green light having an illuminance of 8020 cd/m ² and a current density of 19.2 mA/cm ² .

Apparatus Example 2: Manufacture of an OLED device using the compound of the present invention

The OLED device was fabricated in the same manner as in Device Example 1, except that the compound C-80 was deposited as a hole transport layer having a thickness of 20 nm; and 9-(4-([1,1':3') , 1"-terphenyl"-4-yl)pyrimidin-2-yl)-3-(dibenzo[b,d]thiophen-4-yl)-9H-carbazole introduced into vacuum vapor deposition apparatus In the chamber; the compound D-25 is introduced into another chamber as a dopant material; and the two materials are evaporated at different rates to a deposition amount of 15 weight based on the total amount of the host material and the dopant material. %, to form a light-emitting layer having a thickness of 30 nm on the hole transport layer.

Therefore, the manufactured OLED device exhibited green light having a luminance of 2630 cd/m ² and a current density of 6.4 mA/cm ² .

Comparative Example 1: Fabrication of an OLED device using a conventional electroluminescent compound

The OLED device was fabricated in the same manner as in Device Example 1, except that N,N'-bis(4-biphenyl)-N,N'-bis(4-biphenyl)- was deposited. 4,4'-diaminobiphenyl as a hole transport layer having a thickness of 20 nm; using 4,4'-N,N'-dicarbazole-biphenyl as a host material, and using compound D-15 as a doping a material; a light-emitting layer having a thickness of 30 nm was deposited on the hole transport layer; and a hole blocking layer having a thickness of 10 nm was deposited using bis(2-methyl-8-hydroxyquinoline) 4-phenol aluminum (III).

Therefore, the manufactured OLED device exhibited green light having a luminance of 3350 cd/m ² and a current density of 9.7 mA/cm ² .

It is confirmed that the organic electroluminescent compound of the present invention has high luminous efficiency compared to the conventional material. Further, the organic electric field light-emitting device using the organic electroluminescent compound of the present invention has good luminous efficiency and power efficiency.

Claims (6)

An organic electroluminescent compound, which is represented by the following formula 1: Wherein, L ₁ and L ₂ each independently represent a single bond, a substituted or unsubstituted (C6-C30) extended aryl group, or a substituted or unsubstituted 5 to 30 membered heteroaryl group; Ar ₁ and Ar ₂ each independently represents a substituted or unsubstituted (C6-C30) aryl group, or a substituted or unsubstituted 5 to 30 membered heteroaryl group; X represents an oxygen atom, a sulfur atom, or -CR ₅ R ₆ -; R ₁ to R ₆ each independently represent hydrogen, deuterium, halogen, cyano, carboxy, nitro, hydroxy, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted ( C2-C30) alkenyl, substituted or unsubstituted (C2-C30) alkynyl, substituted or unsubstituted (C1-C30) alkoxy, substituted or unsubstituted (C3-C30) Cycloalkyl, substituted or unsubstituted (C3-C30)cycloalkenyl, substituted or unsubstituted 3 to 7 membered heterocycloalkyl, substituted or unsubstituted (C6-C30) aryl a (C6-C30) aryl group fused to a (C3-C30)cycloalkyl group, or a substituted or unsubstituted 5 to 30 membered heteroaryl group, -NR ₁₁ R ₁₂ , -SiR ₁₃ R _{14 R 15, -SR 16, -OR 17} , -COR 18 , or _{-B (oR 19) (oR 20} ); or the R ₁ to R ₆ taken with the adjacent Group is attached form a monocyclic or polycyclic 3 to 30 of the alicyclic or aromatic ring carbon atom of the ring may be at least one hetero atom selected from nitrogen, oxygen and sulfur of substituted; R ₁₁ to R ₂₀ are each independently Represents hydrogen, deuterium, halogen, cyano, carboxy, nitro, hydroxy, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C2-C30) alkenyl, substituted or Unsubstituted (C2-C30) alkynyl, substituted or unsubstituted (C1-C30) alkoxy, substituted or unsubstituted (C3-C30) cycloalkyl, substituted or unsubstituted (C3-C30)cycloalkenyl, substituted or unsubstituted 3 to 7 membered heterocycloalkyl, substituted or unsubstituted (C6-C30) aryl, or substituted or unsubstituted 5 to 30 membered heteroaryl; or the R ₁₁ to R _{20 are} bonded to an adjacent substituent to form a monocyclic or polycyclic 3 to 30 member alicyclic or aromatic ring, the carbon atom of the ring may be At least one hetero atom selected from nitrogen, oxygen and sulfur; a represents an integer from 1 to 4; when a is an integer of 2 or more, each R ₁ is the same or different; b to d each independently represent an integer from 1 to 3. ; when b, c or d is an integer of 2 or more Each R _2, each R _3, same or different, and each R ₄ lines; the (stretch) heteroaryl containing at least one selected from B, N, O, S, P (= O), Si, and P the heteroatom; And the heterocycloalkyl group contains at least one hetero atom selected from the group consisting of O, S and N. The organic electroluminescent compound according to claim 1, wherein L ₁ , L ₂ , Ar ₁ , Ar ₂ , R ₁ to R ₆ , and R ₁₁ to R ₂₀ are substituted (C1-C30) An alkyl group, a substituted (C2-C30) alkenyl group, a substituted (C2-C30) alkynyl group, a substituted (C1-C30) alkoxy group, a substituted (C3-C30) cycloalkyl group, Substituted (C3-C30)cycloalkenyl, substituted 3 to 7 membered heterocycloalkyl, substituted (extended) aryl, and substituted 5 to 30 member (extended) heteroaryl substituted The groups are each independently a group of at least one substituent selected from the group consisting of hydrazine, halogen, cyano, carboxyl, nitro, hydroxy, (C1-C30)alkyl, halo(C1-C30)alkyl, (C2 -C30) alkenyl, (C2-C30)alkynyl, (C1-C30)alkoxy, (C1-C30)alkylthio, (C3-C30)cycloalkyl, (C3-C30)cycloalkenyl 3 to 7 membered heterocycloalkyl, (C6-C30) aryloxy, (C6-C30) arylthio, unsubstituted or substituted by (C6-C30) aryl 5 to 30 members Heteroaryl, unsubstituted or substituted (C6-C30) aryl, tri(C1-C30)alkyldecyl, tris(C6-C30)aryldecyl, substituted by 5 to 30 membered heteroaryl (C1-C30)alkyl (C6-C30) aryl Alkyl, (C1-C30)alkyl di(C6-C30)aryldecyl, amine, mono or di(C1-C30)alkylamino, mono or di(C6-C30)arylamine, (C1-C30)alkyl(C6-C30)arylamino, (C1-C30)alkylcarbonyl, (C1-C30)alkoxycarbonyl, (C6-C30)arylcarbonyl,di(C6-C30 An aryl boron group, a di(C1-C30)alkylboron group, a (C1-C30)alkyl (C6-C30) aryl boron group, a (C6-C30) aryl (C1-C30) alkyl group, and (C1-C30)alkyl (C6-C30) aryl. The organic electroluminescent compound according to claim 1, wherein L ₁ and L ₂ each independently represent a single bond, a substituted or unsubstituted (C6-C20) extended aryl group, or a substituted or unsubstituted group. Substituted 5 to 15 members of the heteroaryl group; Ar ₁ and Ar ₂ each independently represent a substituted or unsubstituted (C6-C15) aryl group, or a substituted or unsubstituted 5 to 15 member heteroaryl R ₁ to R ₆ each independently represent hydrogen, halogen, substituted or unsubstituted (C1-C15) alkyl, substituted or unsubstituted (C6-C15) aryl, and (C3-C20) a cycloalkyl fused (C6-C15) aryl group, or a substituted or unsubstituted 5 to 15 membered heteroaryl group, -NR ₁₁ R ₁₂ or -SiR ₁₃ R ₁₄ R ₁₅ ; wherein R ₁₁ and R ₁₂ each independently represents a substituted or unsubstituted (C6-C15) aryl group, or a substituted or unsubstituted 5 member to 15 membered heteroaryl group; and R ₁₃ to R ₁₅ each independently represent substituted or unsubstituted Substituted (C1-C10)alkyl, or substituted or unsubstituted (C6-C15) aryl. The organic electroluminescent compound according to claim 1, wherein L ₁ and L ₂ each independently represent a single bond, an unsubstituted or a (C1-C6)alkyl group, a (C6-C15) aryl group, or a (C6-C15) arylamino group substituted (C6-C20) extended aryl group, or an unsubstituted 5 to 10 membered heteroaryl group; Ar ₁ and Ar ₂ each independently represent unsubstituted or via ( C1-C6)alkyl, (C6-C15) aryl, di(C6-C15)arylamino, or (C6-C15)aryl (5 to 10 membered) heteroarylamine (C6- C15) an aryl group, or a 5- to 10-membered heteroaryl group which is unsubstituted or substituted with a (C6-C15) aryl group or a di(C6-C15) arylamino group; R ₁ to R ₆ each independently represent hydrogen, Halogen, unsubstituted (C1-C6)alkyl, unsubstituted or substituted by (C1-C6)alkyl or (C6-C15)aryl (C6-C15) aryl, and (C3-C7) a cycloalkyl fused (C6-C15) aryl group, an unsubstituted 5 to 15 membered heteroaryl group, or -NR ₁₁ R ₁₂ ; wherein R ₁₁ and R ₁₂ each independently represent unsubstituted (C6 -C15) aryl. The organic electroluminescent compound according to claim 1, wherein the compound represented by Formula 1 is selected from the group consisting of: An organic electric field illuminating device comprising the organic electroluminescent compound according to claim 1 of the patent application.