KR101512012B1 - Organic light compound and organic light device using the same - Google Patents

Abstract

The present invention relates to an organic light emitting compound and an organic light emitting device using the same. More particularly, the present invention relates to an organic light emitting device capable of realizing excellent light emitting efficiency, light emission luminance, (ETM), a light-emitting layer (EML), a light-emitting layer (EML), and a light-emitting layer ), A hole transporting layer (HTM), a hole injection layer (HIL), and the like, thereby improving performance such as increasing efficiency and reducing driving voltage, and maximizing the capability as an OLED material.

Description

TECHNICAL FIELD [0001] The present invention relates to an organic electroluminescent compound, and an organic electroluminescent device using the electroluminescent compound.

The present invention relates to an organic light emitting compound and an organic light emitting device using the same.

The organic light emission phenomenon refers to a phenomenon in which light is converted into visible light when electric energy is applied to a specific organic material. That is, when an organic layer is positioned between the anode and the cathode and a voltage is applied between the two electrodes, holes are injected into the anode, and electrons are injected into the anode from the cathode. Electrons and holes injected into the organic material layer recombine to form an exciton, and the exciton falls back to the ground state to emit light.

In the 1950s, Bernanose observed the luminescence from the organic thin film by applying a high alternating voltage to the polymer thin film containing the organic dye. In 1965, a current was applied to the anthracene single crystal to generate singlet exciton To obtain blue fluorescence.

As a method for efficiently forming an organic EL device, research has been conducted to manufacture an organic material layer in a device in a multilayer structure instead of a single layer. In 1987, a layered organic EL device was developed by Tang divided into a hole layer and a functional layer of a light emitting layer. Most currently used organic EL devices include a substrate, an anode, a hole injecting layer selectively accepting holes from the anode, a hole transporting layer selectively transferring holes, a light emitting layer emitting light by recombination of holes and electrons, An electron transport layer for transporting electrons, an electron injection layer for receiving electrons from the cathode, and a cathode.

The reason why the organic EL devices are formed in a multilayer structure is that the moving speeds of holes and electrons are different from each other, so that if a proper hole injection layer, a hole transport layer, an electron transport layer, and an electron injection layer are formed, This is because a balance of holes and electrons in the device can be balanced to increase the luminous efficiency.

The electrons injected from the electron injecting layer and the holes injected from the hole injecting layer recombine to form excitons in the light emitting layer. The excitons fall from the singlet excitation state to the base state and the light emission is referred to as 'fluorescence'. In the triplet excited state, Is called phosphorescence. Theoretically, when carriers are recombined in the light emitting layer and excitons are generated, singlet and triplet excitons are generated at a ratio of 1: 3. When phosphorescence emission is used, it is possible to increase the internal quantum efficiency to 100%.

In general, carbazole ring compounds such as 4,4-dicarbazolybiphenyl (CBP) are the most widely known phosphorescent host materials. As phosphorescent guest materials, metal complex compounds containing a heavy atom such as Ir or Pt are widely used.

However, CBP, which is used as a phosphorescent host material, has a low glass transition temperature (Tg) of about 110 ° C and crystallization in the device easily occurs, and thus the lifetime of the organic electroluminescent device is extremely short as about 150 hours.

Also disclosed are amine compounds in which carbazole rings are introduced into the molecule as organic luminescent compounds, and these compounds are compounds having a molecular structure in which a nitrogen atom is bonded to the C3 position of the carbazole ring. However, when the carbazole-based compound is used for a hole transporting layer, the barrier for injecting holes into the light emitting layer becomes large, There is a problem that the driving voltage of the EL element becomes high.

The first technical problem to be solved by the present invention is to provide a novel carbazole-based organic electroluminescent device capable of being applied as a phosphorescent green host material, a fluorescent green host material, a hole injecting layer material, or a hole transporting layer material of an organic light emitting device, Compound. ≪ / RTI >

A second object of the present invention is to provide an organic EL device including the novel carbazole-based organic luminescent compound, which has a low driving voltage and improved luminous efficiency, luminance, thermal stability and device life.

The present invention is characterized by a carbazole-based organic light-emitting compound represented by the following formula (F).

[Chemical Formula F]

In Formula (F) above,

또는

이고, 또는 R₁,R₂,R₃,및 R₄는 서로 이웃하는 기끼리 결합하여 5 내지 10원자로 구성된 축합고리(fused ring)를 형성할 수 있고;R ₁ , R ₂ , R ₃ , and R ₄ , which are the same or different from each other,

or

Or R ₁ , R ₂ , R ₃ , and R ₄ may bond to each other to form a fused ring composed of 5 to 10 atoms;

X is a single bonding line, or -O-, -S-, -NH-, -N- phenyl, -Si (C ₁ -C _{6 alkyl) 2 -, - CH 2 -} , -C (C 1 -C 6 Alkyl) ₂ -;

또는

일 수 있고; 또는LP ₁

or

Lt; / RTI > or

이고;L is

ego;

P ₁ and P ₂ are the same or different from each other

이고;

ego;

A is selected from the group consisting of C ₁ -C ₄₀ alkane, C ₅ -C ₄₀ cycloalkane, C ₂ -C ₄₀ alkene, C ₂ -C ₄₀ alkyne, C ₆ -C ₄₀ aryl, tri (C ₁ -C ₄₀ alkyl) (C ₁ -C ₄₀ alkyl) silane, tri (C ₆ -C ₄₀ aryl) silane, and tetra (C ₆ -C ₄₀ aryl) silane;

Het comprises 1 to 4 heteroatoms selected from mono (C ₆ -C ₄₀ aryl) amines, di (C ₆ -C ₄₀ aryl) amines, and N, O, S, P, and Si, A C ₃ -C ₄₀ heteroaryl of a triple ring and a C ₃ -C ₄₀ heterocycloalkyl;

R ^a is C ₁ -C ₄₀ alkyl, C ₆ -C ₄₀ aryl group, -O- (C ₆ -C ₄₀ aryl), -S- (C ₆ -C ₄₀ aryl), - (C ₆ -C ₄₀ aryl _{alkylene) P (O) (C 6} -C 40 _{aryl) 2, -NH (C 6 -C} 40 aryl), -N (C ₆ -C _{40 aryl) 2, -Si (C 6 -C} 40 aryl) ₃ , Or a C ₃ -C ₄₀ heteroaryl group containing 1 to 4 nitrogen atoms (N), m is an integer of 0 to 4 as the number of the substituent Ra;

는

를 나타낸다.In the definition of L above

The

.

The present invention also provides a plasma display panel comprising: a first electrode; A second electrode; And at least one organic layer between the first electrode and the second electrode, wherein the organic layer comprises a carbazole-based organic light-emitting compound represented by Formula (F).

The organic EL device including the carbazole-based organic luminescent compound according to the present invention can realize high luminescence efficiency, high luminescence brightness, and remarkably improved luminescence lifetime.

Accordingly, the present invention provides a novel organic light emitting compound and an organic light emitting device comprising the compound.

Hereinafter, the present invention will be described in more detail.

While the present invention has been described in connection with what is presently considered to be the most practical and preferred embodiment, it is to be understood that the invention is not limited to the disclosed embodiments. It is to be understood, however, that the invention is not intended to be limited to the particular forms disclosed, but on the contrary, is intended to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The singular expressions include plural expressions unless the context clearly dictates otherwise. In this application, the terms " comprises, " or " comprising " and the like are used to specify that a feature, a number, a step, an operation, an element, a part, But do not preclude the presence or addition of one or more other features, numbers, steps, operations, components, parts, or combinations thereof.

Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.

Terms such as those defined in commonly used dictionaries are to be interpreted as having a meaning consistent with the contextual meaning of the related art and are to be interpreted as either ideal or overly formal in the sense of the present application Do not.

The present invention relates to an organic electroluminescent compound (EML), a hole transporting layer (HTM), a hole transporting layer (HTL), and a hole transporting layer HIL), and to develop materials that improve performance such as efficiency and drive voltage reduction, and maximize their ability as an OLED material.

In the present specification, the organic luminescent compound means a compound used in an organic luminescent device, and is not necessarily limited in its range of application, and its application range is not limited to the organic luminescent layer, It can be used for any layer constituting the light emitting element.

In this specification, the terms 'light emitting compound' and 'light emitting device' are used to cover the case where the present invention is applied to both an organic light emitting device and a device for solar power generation regardless of a dictionary or customary definition It is a selected term.

An organic light emitting device according to a first aspect of the present invention includes: a first electrode; A second electrode; And at least one organic film between the first electrode and the second electrode, wherein the organic film comprises an organic light emitting compound represented by the following formula (F).

[Chemical Formula F]

In Formula (F) above,

또는

이고, 또는 R₁,R₂,R₃,및 R₄는 서로 이웃하는 기끼리 결합하여 5 내지 10원자로 구성된 축합고리(fused ring)를 형성할 수 있고;R ₁ , R ₂ , R ₃ , and R ₄ , which are the same or different from each other,

or

Or R ₁ , R ₂ , R ₃ , and R ₄ may bond to each other to form a fused ring composed of 5 to 10 atoms;

X is a single bonding line, or -O-, -S-, -NH-, -N- phenyl, -Si (C ₁ -C _{6 alkyl) 2 -, - CH 2 -} , - C (C 1 -C 6 Alkyl) ₂ -;

또는

일 수 있고; 또는LP ₁

or

Lt; / RTI > or

이고;L is

ego;

P ₁ and P ₂ are the same or different from each other

이고;

ego;

A is selected from the group consisting of C ₁ -C ₄₀ alkane, C ₅ -C ₄₀ cycloalkane, C ₂ -C ₄₀ alkene, C ₂ -C ₄₀ alkyne, C ₆ -C ₄₀ aryl, tri (C ₁ -C ₄₀ alkyl) (C ₁ -C ₄₀ alkyl) silane, tri (C ₆ -C ₄₀ aryl) silane, and tetra (C ₆ -C ₄₀ aryl) silane;

Het comprises 1 to 4 heteroatoms selected from mono (C ₆ -C ₄₀ aryl) amines, di (C ₆ -C ₄₀ aryl) amines, and N, O, S, P, and Si, A C ₃ -C ₄₀ heteroaryl of a triple ring and a C ₃ -C ₄₀ heterocycloalkyl;

Ra represents a C ₁ -C ₄₀ alkyl group, a C ₆ -C ₄₀ aryl group, -O- (C ₆ -C ₄₀ aryl), -S- (C ₆ -C ₄₀ aryl), - (C ₆ -C ₄₀ arylene _{) P (O) (C 6} -C 40 _{aryl) 2, -NH (C 6 -C} 40 aryl), -N (C ₆ -C _{40 aryl) 2, -Si (C 6 -C} 40 aryl) _3, Or a C ₃ -C ₄₀ heteroaryl group containing 1 to 4 nitrogen atoms (N), m is an integer of 0 to 4 as the number of the substituent Ra;

는

를 나타낸다.In the definition of L above

The

.

The inventors of the present invention have developed various derivatives of R ₁ , R ₂ , R ₃ , R ₄ , X, P ₁ , P ₂ and L as substituents of the organic light emitting compound represented by the above formula (F) An organic light emitting compound that can be used as various organic films between a first electrode and a second electrode such as a light emitting layer (EML), a light emitting layer (EML), and a hole transporting layer (HTM) It has been found that it is possible to improve the performance such as the increase of the efficiency and the reduction of the driving voltage and the ability of the OLED material to be maximized and in particular the luminescence lifetime to be remarkably improved when applied to optical devices and optical compounds for photovoltaic power generation It is expected that excellent power generation efficiency can be obtained.

Hereinafter, the organic electroluminescent compound represented by Formula F will be described with reference to the organic electroluminescent device, but the present invention should not be construed as being limited thereto.

The organic electroluminescent compound represented by Formula F is suitable as a material for forming an organic film interposed between the first electrode and the second electrode of the organic light emitting device. The organic light emitting compound represented by Formula F is suitable for use in an organic layer of an organic light emitting device, particularly, a hole transporting layer, a hole injecting layer, an electron transporting layer, or a light emitting layer, and is used as a dopant material as well as a host material. The organic light emitting compound represented by Formula F provides a green color and is suitable for use in a light emitting device such as white.

A - In a preferred embodiment in the organic light-emitting compound represented by the general formula F, wherein X is a single bonding line, or _{-C (CH 3) (CH 3} ).

, 또는

이다. 또한, 바람직한 구현예로서 상기 R₁과 R₂,R₂와 R₃,또는 R₃과 R₄가 서로 결합하여 5각형 또는 6각형의 축합고리(fused ring)을 형성하는 것이다.In a preferred embodiment, R ₁ , R ₂ , R ₃ , and R ₄ are the same or different and each is a hydrogen atom in the organic light emitting compound represented by Formula F above. In a preferred embodiment, R ₁ , R ₂ , and R ₄ are hydrogen atoms, and R ₃ is

, or

to be. In a preferred embodiment, R ₁ and R ₂ , R ₂ and R ₃ , or R ₃ and R ₄ are bonded to each other to form a pentagonal or hexagonal fused ring.

, 또는

이다. 또한, 바람직한 구현예로서 상기 L-P₁가 하기의 그룹으로부터 선택된다 :In a preferred embodiment in the organic electroluminescent compounds represented by Chemical Formula F, wherein the LP ₁

, or

to be. Also, as a preferred embodiment, the LP < ₁ > is selected from the group:

(Wherein A, Het, R &^lt; a >, and m are each as defined above)

In a preferred embodiment of the organic electroluminescent compound represented by Formula F, A is selected from the group consisting of benzene, biphenyl, bis (toluene), naphthalene, 1- (naphthalen-5-yl) naphthalene, 1- (1-phenylnaphthalene- 4-yl) naphthalene, fluorene, spirobifluorene, triphenyl (biphenyl) silane, and tetraphenylsilane. Also, in a preferred embodiment, A is an aliphatic mono- or di-group derived from the group consisting of methane, ethane, ethene, ethyne, cyclohexane, piperidine, and piperazine.

(이때, X₁은 -O-, -S-, -NH-, -N-페닐, -Si(C₁-C₆알킬)₂-,-CH₂-,-C(C₁-C₆알킬)₂-,-CH₂CH₂-,또는 -CH=CH-이고,In a preferred embodiment, the organic electroluminescent compound represented by the above formula (F) is at least one selected from the group consisting of phenylamine, diphenylamine, furan, thiophene, pyrrole, thiazole, thiadiazole, oxazole, oxadiazole, imidazole, The present invention relates to a method for producing a compound represented by the general formula (1), wherein the compound is selected from the group consisting of a pyrazole, a triazole, a pyridine, a pyrimidine, pyrazine, pyridazine, triazine, tetrazine, benzothiophene, indole, indolizine, benzoimidazole, Pyridine, pyridine, pyrazinopyrazine, acridine, 9, 9, 10, 11, 12, 13, 14, Dihydro-9,10-dimethylacridine, phenanthridine, phenanthroline, pyridoindole, pyridinyltriazole, pyrimidinyltriazole, pyrazinyltriazole, triazinyltriazole, triazolopyridine ,

(Wherein, X ₁ is -O-, -S-, -NH-, -N- phenyl, -Si (C ₁ -C _{6 alkyl) 2 -, - CH 2 -} , - C (C 1 -C 6 alkyl ) ₂ -, - CH ₂ CH ₂ -, or -CH = CH-,

는

이다.)으로 이루어진 군으로부터 유래된 1가기 또는 2가기이다.

The

). ≪ / RTI >

In a preferred embodiment of the organic electroluminescent compound represented by Formula F, R ^a is ^a group selected from the group consisting of a tert-butyl group, a phenyl group, a biphenyl group, -O-phenyl, -S-phenyl, -C ₆ H ₄ -P (O) (Phenyl) ₂ , -Si (phenyl) ₃ , -Si (biphenyl) (phenyl) ₂ , -NH (phenyl), -N (phenyl) ₂ , pyridinyl, pyrazinyl or triazole.

In a preferred embodiment of the organic light-emitting compound represented by the above formula (F), P ₂ is selected from the following group.

(Wherein R ^a is as defined above and m is an integer of 0 to 4 as the number of substituents R ^a )

According to one embodiment of the present invention, the organic luminescent compound used in the organic luminescent device of the present invention has carbazole as a basic skeleton. Specifically, compounds represented by the following formulas (1) to 252, although the invention is not so limited:

[First group (group)]

The organic electroluminescent compound represented by Formula F according to the present invention can be synthesized using conventional synthetic methods, and a more detailed synthesis route of the compound can be described in Representative Synthesis Examples 1 to 4 below.

The organic luminescent compound represented by Formula F is suitable for use in an organic layer of an organic light emitting diode, particularly, a hole transport layer, a hole injection layer, an electron transport layer, or a light emitting layer. The structure of the organic light emitting device according to the present invention is very diverse. The organic EL device may further include at least one layer selected from the group consisting of a hole injecting layer, a hole transporting layer, a hole blocking layer, an electron blocking layer, an electron transporting layer, and an electron injecting layer between the first electrode and the second electrode.

More specifically, the present invention provides an organic electroluminescent device, wherein the organic electroluminescent device comprises: a first electrode; A second electrode; And at least one organic compound layer interposed between the first electrode and the second electrode, wherein the organic compound layer comprises at least one organic electroluminescent compound selected from Formula (F).

The organic electroluminescent device according to the present invention may further include at least one compound represented by the above formula (F) and at the same time, a conventional host material, a conventional dopant material, or a mixture thereof.

The organic electroluminescent device according to the present invention comprises the organic compound layer as a light emitting layer, wherein the light emitting layer comprises at least one phosphorescent dopant as at least one organic electroluminescent compound selected from compounds represented by the general formula (F) The dopant is not particularly limited.

In the organic electroluminescent device of the present invention, at least one compound selected from the group consisting of an arylamine-based compound and a styrylarylamine-based compound, which contains at least one organic electroluminescent compound selected from the compound represented by the above formula (F) .

Further, in the organic light emitting device of the present invention, in addition to one or more organic luminescent compounds selected from the compounds represented by the above formula (F) in the organic layer, Group 1, Group 2, Group 4, Group 5 transition metal, Group lanthanide metal, The organic compound layer may further include at least one metal or complex compound selected from the group consisting of an organic metal of the element, and the organic compound layer may include a light emitting layer and a charge generating layer.

In addition, an organic electroluminescent device emitting white light by simultaneously including at least one common organic light emitting layer emitting blue, red or green light in addition to the organic light emitting compound may be formed in the organic material layer.

More specifically, in an embodiment of the organic light emitting device according to the present invention, the organic light emitting device may have a structure including a first electrode / a hole injection layer / a light emitting layer / an electron transport layer / an electron injection layer / The organic light emitting device may have a structure including a first electrode / a hole injection layer / a hole transporting layer / a light emitting layer / an electron transporting layer / an electron injecting layer / a second electrode. Further, the organic light emitting device may include a first electrode / a hole injecting layer / / Light emitting layer / hole blocking layer / electron transporting layer / electron injecting layer / second electrode.

At this time, one or more of the electron transporting layer, the light emitting layer, the hole injecting layer, or the hole transporting layer may include an organic light emitting compound according to the present invention.

The light emitting layer of the organic light emitting device according to the present invention may include a phosphorescent or fluorescent dopant including red, green, blue or white. The phosphorescent dopant may be an organometallic compound containing at least one element selected from the group consisting of Ir, Pt, Os, Ti, Zr, Hf, Eu, Tb and Tm. In addition, the compound according to the present invention can also be used as a fluorescent dopant in the light emitting layer.

Hereinafter, a method of manufacturing an organic light emitting device according to the present invention will be described in detail. First, a first electrode material having a high work function is formed on a substrate by a vapor deposition method, a sputtering method, or the like to form a first electrode. The first electrode may be an anode. Here, as the substrate, a substrate used in a common organic light emitting device is used, and a glass substrate or a transparent plastic substrate having excellent mechanical strength, thermal stability, transparency, surface smoothness, ease of handling and waterproofness is preferable. As the material for the first electrode, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO ₂ ), zinc oxide (ZnO) or the like which is transparent and excellent in conductivity is used.

Next, a hole injection layer (HIL) may be formed on the first electrode by various methods such as a vacuum deposition method, a spin coating method, a casting method, and an LB method.

When the hole injection layer is formed by the vacuum deposition method, the deposition conditions vary depending on the compound used as the material of the hole injection layer, the structure and the thermal characteristics of the desired hole injection layer, and the like. In general, A degree of vacuum of 10 < ^-5 > to 10 < ^-3 > torr, a deposition rate of 0.01 to 100 ANGSTROM / sec, and a film thickness of 100 ANGSTROM to 1 mu m.

When the hole injecting layer is formed by spin coating, the coating conditions vary depending on the compound used as the material of the hole injecting layer, the structure and the thermal properties of the desired hole injecting layer, and preferably from about 2000 rpm to 5000 rpm The coating speed and the heat treatment temperature for removing the solvent after coating are preferably selected in a temperature range of about 80 to 200 캜.

The hole injection layer material may be an organic light emitting compound represented by Formula F as described above.

Alternatively, phthalocyanine compounds such as copper phthalocyanine disclosed in U.S. Patent No. 4,356,429 or starburst amine derivatives such as TCTA, m-MTDATA, and m-MTDATA described in Advanced Material, 6, p.677 (1994) (2-TNATA), polyaniline / dodecylbenzenesulfonic acid (Pani / DBSA), which is a soluble conductive polymer, (PEDOT / PSS), polyaniline / camphorsulfonic acid (PANI / CSA) or polyaniline / poly (4-styrenesulfonate) (PANI / PSS ), And the like can be used.

The thickness of the hole injection layer may be about 100 A to about 10000 A, and preferably about 100 A to about 1000 A. When the thickness of the hole injection layer is less than 100 ANGSTROM, hole injection characteristics may be degraded. If the thickness of the hole injection layer is more than 10000 ANGSTROM, the driving voltage may increase.

Alternatively, the hole injection layer may be formed by a vacuum vapor deposition method. The specific deposition conditions vary depending on the compound used, but are selected from substantially the same range of conditions as the formation of a general hole injection layer. For example, N, N-bis- [4- (di-methtolylamino) phenyl] -N, N-biphenyl-4,4-diamine (DNTPD) and the like can be used.

Next, a hole transport layer (HTL) may be formed on the hole injection layer by various methods such as a vacuum deposition method, a spin coating method, a casting method, and an LB method. In the case of forming the hole transporting layer by the vacuum deposition method and the sputtering method, the deposition conditions and the coating conditions vary depending on the compound used, but are generally selected from substantially the same range of conditions as the formation of the hole injection layer.

The hole transport layer material may include an organic light emitting compound represented by Formula (F) as described above. Examples of known hole transporting materials include carbazole derivatives such as N-phenylcarbazole and polyvinylcarbazole, N, N'-bis (3-methylphenyl) -N, N'- 1-biphenyl] -4,4'-diamine (TPD), and N, N'-di A typical amine derivative, and the like. The thickness of the hole transporting layer may be about 50 A to 1000 A, preferably 100 A to 600 A. When the thickness of the hole transporting layer is less than 50 ANGSTROM, the hole transporting property may be deteriorated. When the thickness of the HTL is more than 1000 ANGSTROM, the driving voltage may increase.

Next, a light emitting layer (EML) may be formed on the hole transporting layer by a method such as a vacuum evaporation method, a spin coating method, a casting method, or an LB method. When a light emitting layer is formed by a vacuum deposition method and a spin coating method, the deposition conditions vary depending on the compound used, but generally, the conditions are substantially the same as those for forming the hole injection layer.

The light emitting layer may include the compound represented by Formula F according to the present invention as described above. At this time, the compound represented by the above formula (F) can be used together with a suitable known host material or can be used together with a known dopant material. It is also possible to use the compound represented by the above formula (F) alone.

Examples of the host material usable in combination with the compound represented by Formula F include tris (8-hydroxyquinolate aluminum (Alq3), 4,4'-N, N'-dicarbazole- CBP), poly (n-vinylcarbazole) (PVK), etc. The host material may include an asymmetric anthracene derivative represented by the following formula (i), an asymmetric monoanthracene derivative represented by the following formula An asymmetric pyrene derivative represented by the following formula (iv), an asymmetric anthracene derivative represented by the following formula (iv), an anthracene derivative represented by the following formula (v), an anthracene derivative represented by the following formula (vi), a spirofluorene derivative represented by the following formula A condensed ring-containing compound represented by the formula (X), a fluorene compound represented by the following formula (X), an anthracene center skeleton represented by the following formula (X) Or a compound having an anthracene central skeleton represented by the following formula (xi) wherein A ₁ and A ₂ in the above formula (x) are substituted with different groups.

(I)

In formula i, Ar is a substituted or unsubstituted C ₁₀ ~C ₅₀ condensed aryl group, in which p is 1 to 100; Ar 'is a substituted or unsubstituted C ₆ ~C ₅₀ aryl group; X is a substituted or unsubstituted C ₆ ~C ₅₀ aryl group, a substituted or unsubstituted heteroaryl group can be unsubstituted 5 to 50 nuclear atoms, a substituted or unsubstituted alkyl group of C ₁ ~C ₅₀ ring, a substituted or unsubstituted an alkoxy group of C ₁ ~C _50, a substituted or unsubstituted aralkyl group unsubstituted C ₆ ~C _50, a substituted or unsubstituted 6 to 50 nuclear atoms aryloxy group, a substituted or unsubstituted nuclear atoms of 6 to 50 A substituted or unsubstituted C ₁ to C ₅₀ alkoxycarbonyl group, a carboxyl group, a halogen atom, a cyano group, a nitro group, or a hydroxyl group; a, b and c are each independently an integer of 0 to 4; n is an integer of 1 to 3, and when n is 2 or 3, [] may be the same or different.

(Ii)

In the above formula (ii), Ar ¹ and Ar ² are each independently a substituted or unsubstituted C ₆ -C ₅₀ aryl group; m and n are each an integer of 1 to 4, provided that when m = n = 1 and Ar ¹ and Ar ² have a symmetric bond to the benzene ring, Ar ¹ and Ar ² are not the same and m or n Is an integer of 2 to 4, m and n are different integers; Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom, a substituted or unsubstituted C ₆ to C ₅₀ aryl group, substituted or unsubstituted heteroaryl group can be substituted in the 5 to 50, the ring nucleus atoms or unsubstituted alkyl group-substituted C ₁ ~C _50, a substituted or unsubstituted C ₃ ~C ₅₀ cycloalkyl group, a substituted or unsubstituted C ₁ ~ C ₅₀ alkoxy group, a substituted or unsubstituted C ₆ ~C ₅₀ aralkyl group, a substituted or unsubstituted 5 to 50 nuclear atoms aryloxy, substituted or unsubstituted aryl of 6 to 50 nuclear atoms of Cy A substituted or unsubstituted C ₁ to C ₅₀ alkoxycarbonyl group, a substituted or unsubstituted silyl group, a carboxyl group, a halogen atom, a cyano group, a nitro group or a hydroxyl group.

(Iii)

In the above formula (iii), Ar and Ar 'are each independently a substituted or unsubstituted aromatic C _{6 to} C ₅₀ aryl group; L and L 'are each independently a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthalenylene group, a substituted or unsubstituted fluorenylene group or a substituted or unsubstituted dibenzylphenylene group; m is an integer from 0 to 2; n is an integer from 1 to 4; s is an integer from 0 to 2; t is an integer from 0 to 4; And L or Ar is bonded to any one of the C1 to C5 positions of the pyrene and L 'or Ar' is bonded to any one of the C6 to C10 positions of the pyrene,

Provided that Ar, Ar ', L and L' satisfy the following (1) or (2) when n + t is an even number:

(1) Ar ≠ Ar 'and / or L ≠ L' (wherein ≠ represents a group of different structure)

(2) when Ar = Ar 'and L = L'

(2-1) m? S and / or n? T, or

(2-2) When m = s and n = t,

(2-2-1) L and L ', or pyrene is bonded to other bonding sites on Ar and Ar'

(2-2-2) When L and L 'or pyrene are bonded at the same bonding positions on Ar and Ar', the substitution positions of L and L 'or Ar and Ar' in the pyrene are C1 and C6 Position, or C2 or C7 position.

[Chemical Formula (iv)

In Formula ⅳ, A ¹ and A ² are each independently a substituted or unsubstituted C ₁₀ ~C2 ₀ condensed aryl group of; Ar ¹ and Ar ² are each independently a hydrogen atom or a substituted or unsubstituted C ₆ -C ₅₀ aryl group; Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom, a substituted or unsubstituted C ₆ to C ₅₀ aryl group, A substituted or unsubstituted heteroaryl group having 5 to 50 nuclear atoms, a substituted or unsubstituted C ₁ to C ₅₀ alkyl group, a substituted or unsubstituted C ₃ to C ₅₀ cycloalkyl group, a substituted or unsubstituted C ₁ ~C ₅₀ alkoxy group, a substituted or unsubstituted C ₆ ~C ₅₀ aralkyl group, a substituted or unsubstituted 6 to 50 nuclear atoms aryloxy group, a substituted or unsubstituted aryl of 6 to 50 nuclear atoms A substituted or unsubstituted C ₁ to C ₅₀ alkoxycarbonyl group, a substituted or unsubstituted silyl group, a carboxyl group, a halogen atom, a cyano group, a nitro group or a hydroxyl group; Ar ¹ , Ar ² , R ⁹ and R ¹⁰ are substituents on the condensed aryl group and may be substituted by a plurality of two or more, which may be adjacent to each other to form a saturated or unsaturated ring; However, the case where groups symmetrical with respect to the XY axis shown in the anthracene phase are bonded to the C9 and C10 positions of the anthracene mother nucleus are excluded.

(V)

Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom, a C _{1 to} C ₅₀ alkyl group, a C of ₃ ~C ₅₀ cycloalkyl group, a substituted or unsubstituted C ₆ ~C ₅₀ aryl group, a substituted or unsubstituted C ₁ ~C ₅₀ alkoxy group, a substituted or unsubstituted C ₆ ~C ₅₀ aryl oxy group , A substituted or unsubstituted C ₁ to C ₅₀ alkylamino group, a substituted or unsubstituted C ₂ to C ₅₀ alkenylene group, a substituted or unsubstituted C ₆ to C ₅₀ arylamino group, a substituted or unsubstituted C ₅ ~C ₅₀ hetero aryl group or a substituted or represents a heterocycle of the unsubstituted C ₅ ~C _50; a and b each independently represent an integer of 1 to 5, provided that when they are two or more, R ^{1 s} or R ^{2 s} may be the same or different and R ^{1 s} or R ^{2 s} may be bonded to each other to form a ring , And R ³ and R ⁴ , R ⁵ and R ⁶ , R ⁷ and R ⁸ , R ⁹ and R ¹⁰ may be bonded to each other to form a ring; L ¹ is a single bond, -O-, -S-, -N (R ) - ( wherein R is an aryl group of C ₁ ~C ₅₀ alkyl group or a substituted or unsubstituted C ₆ ~C ₅₀ a), C ₂ ~ for C ₅₀ alkylene group or a C ₆ ~C ₅₀ represents an arylene.

(Vi)

Wherein R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ each independently represent a hydrogen atom, a C _{1 to} C ₅₀ alkyl group, C C _{3 to} C ₅₀ cycloalkyl, C _{6 to} C ₅₀ aryl, C _{1 to} C ₅₀ alkoxy, aryloxy of 6 to 50 nucleus atoms, C _{1 to} C ₅₀ alkylamino, C _{6 to} C _A substituted or unsubstituted arylamino group having 5 to 50 ring atoms, a heteroaryl group having 5 to 50 ring atoms having a substituted or unsubstituted hetero ring group, or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms; c, d, e, and f each independently represent an integer of 1 to 5, and when two or more thereof are present, R ¹¹ , R ¹² , R ¹⁶ or R ¹⁷ may be the same or different, and R ¹¹ , R ¹² , R ¹⁶ or R ¹⁷ may be bonded to each other to form a ring, or R ¹³ and R ¹⁴ , R ¹⁸ and R ¹⁹ may be bonded to each other to form a ring; L ² represents a single bond, -O-, -S-, -N (R ) - ( wherein R is an aryl group of C ₁ ~C ₅₀ alkyl group or a substituted or unsubstituted C ₆ ~C ₅₀ a), C ₂ ~ for C ₅₀ alkylene group or a C ₆ ~C ₅₀ represents an arylene.

[Chemical Formula I]

In the above formula, A ⁵ , A ⁶ , A ⁷ and A ⁸ are each independently a substituted or unsubstituted biphenyl group or a substituted or unsubstituted naphthyl group.

[Chemical Formula I]

Wherein A ⁹ , A ¹⁰ , A ¹¹ , A ¹² , A ¹³ and A ¹⁴ are each independently a substituted or unsubstituted biphenyl group or a substituted or unsubstituted naphthyl group, Or more condensed aromatic ring; R ²¹ , R ²² and R ²³ each independently represents a hydrogen atom, a C _{1 to} C ₆ alkyl group, a C _{3 to} C ₆ cycloalkyl group, a C _{1 to} C ₆ alkoxy group, a C _{5 to} C ₁₈ aryloxy group , A C _{7 to} C ₁₈ aralkyloxy group, a C _{5 to} C ₁₆ arylamino group, a nitro group, a cyano group, an C _{1 to} C ₆ ester group or a halogen atom.

[Chemical Formula I]

Wherein R ₁ and R ₂ are each independently a hydrogen atom, a substituted or unsubstituted C ₁ -C ₅₀ alkyl group, a substituted or unsubstituted C ₆ -C ₅₀ aralkyl group, a substituted or unsubstituted C ₆ ~C ₅₀ aryl group, a substituted or unsubstituted substituted group, the number of nuclear atoms of 5 to 50 ring heterocycle or represents an amino group, a cyano group or a halogen atom unsubstituted, each other R _1, which is bonded to another fluorene And R _{2 's} may be the same or different from each other, and R ₁ and R ₂ bonded to the same fluorene group may be the same or different from each other; R ₃ and R ₄ are each independently a hydrogen atom, a substituted or unsubstituted C ₁ to C ₅₀ alkyl group, a substituted or unsubstituted C ₆ to C ₅₀ aralkyl group, a substituted or unsubstituted C ₆ to C ₅₀ An aryl group or a substituted or unsubstituted heterocyclic group having 5 to 50 nuclear atoms and R ₃ and R ₄ bonded to other fluorene groups may be the same or different and R ₃ and R ₄ may be the same or different from each other; Ar ₁ and Ar ₂ are a substituted or unsubstituted condensed polycyclic aromatic group having a total of three or more benzene rings or a condensed polycyclic hetero ring having three or more benzene rings and a heterocyclic ring bonded to a fluorene group, And Ar ₁ and Ar ₂ may be the same or different from each other; n represents an integer of 1 to 10;

[Formula x]

In formula (x), A ₁ and A ₂ are each independently a substituted or unsubstituted C ₆ -C ₂₀ aryl group or a group derived therefrom, and the aryl group is a substituted or unsubstituted C ₆ -C ₅₀ aryl A substituted or unsubstituted C ₁ to C ₅₀ alkyl group, a substituted or unsubstituted C ₃ to C ₅₀ cycloalkyl group, a substituted or unsubstituted C ₁ to C ₅₀ alkoxy group, a substituted or unsubstituted C ₆ of ~C ₅₀ aralkyl group, a substituted or unsubstituted 5 to 50 nuclear atoms aryloxy, substituted or unsubstituted come in the number of nuclear atoms of 5 to 50 ring Cy aryl, substituted or unsubstituted C ₁ ~C ₅₀ of An alkoxycarbonyl group, a substituted or unsubstituted silyl group, a carboxyl group, a halogen atom, a cyano group, a nitro group and a hydroxyl group, and may be substituted with two or more substituents When substituted, these substituents May be the same or different from each other and the adjacent substituents may be bonded to each other to form a saturated or unsaturated cyclic structure; Each of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ is independently a hydrogen atom, a substituted or unsubstituted C ₆ to C ₅₀ aryl group, a substituted or unsubstituted nucleus A substituted or unsubstituted C ₁ to C ₅₀ alkyl group, a substituted or unsubstituted C ₃ to C ₅₀ cycloalkyl group, a substituted or unsubstituted C ₁ to C ₅₀ alkoxy group , A substituted or unsubstituted C ₆ to C ₅₀ aralkyl group, a substituted or unsubstituted aryloxy group having 5 to 50 nuclear atoms, an arylthio group having 5 to 50 substituted or unsubstituted nuclear atoms, hwandoen C ₁ ~C ₅₀ alkoxy carbonyl group, the substituted or between unsubstituted silyl group, a carboxyl group, a halogen atom, a cyano group and is selected from the group and a hydroxyl group, nitro.

(Xi)

In formula (xi), A ₁ , A ₂ , R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are each independently as defined in formula x above, The groups which are symmetrical with respect to the XY axis shown in the anthracene phase are not bonded to the C9 and C10 positions of the anthracene.

Among the host materials described above, an anthracene derivative is preferable, a monoanthracene derivative is more preferable, and an asymmetric anthracene derivative is particularly preferable.

As a dopant material usable in combination with the compound represented by the above formula (F), IDE102, IDE105 available from Idemitsu Co., Ltd. and C545T available from Hayashibara Co., Ltd. can be used as a fluorescent dopant, and red phosphorescence Dopant PtOEP, UDC RD61, green phosphorescent dopant Ir (PPy) 3 (where PPy is 2-phenylpyridine), F2Irpic as a blue phosphorescent dopant, and RD 61 as a red light dopant of UDC. N-methylquinacridone (MQD), coumarine derivatives and the like can also be used. Further, a metal-ligand complex compound represented by the following formula (a) may also be used.

(A)

M ¹ L ¹⁰¹ L ¹⁰² L ¹⁰³

In Formula (a), M ¹ is selected from the group consisting of Group 7, Group 8, Group 9, Group 10, Group 11, Group 13, Group 14, Group 15, and Group 16 metal elements on the periodic table; L ¹⁰¹ , L ¹⁰² and L ¹⁰³ are each selected from the following structures as ligands;

,

또는

이며, R₂₃₁내지 R₂₄₂는 서로 독립적으로 수소, 중수소, 할로젠이 치환되거나 치환되지 않은 C₁∼C₃₀의 알킬기, C₁∼C₃₀의 알콕시기, 할로젠이 치환 또는 비치환된 C₆∼C₃₀의 아릴기, 시아노가 치환 또는 비치환된 C₅∼C₃₀의 시클로알킬기이거나, 인접한 치환체와 C₃∼C₁₂의 알킬렌 또는 C₃∼C₁₂의 알케닐렌으로 연결되어 스피로 고리 또는 축합고리를 형성할 수 있거나, R₂₀₇또는 R₂₀₈과 C₃∼C₁₂의 알킬렌 또는 C₃∼C₁₂의 알케닐렌으로 연결되어 포화 또는 불포화의 축합고리를 형성할 수 있다.At this time, the R _201, R _202, and R ₂₀₃ each represent a hydrogen atom, an alkyl group with or without halogen substituent _{C 1 ~C 30, C 1 ~C} 30 alkyl is optionally substituted C ₁ ~C ₅₀ of An aryl group, or a halogen atom; R ₂₀₄ to R ₂₁₉ independently represent a hydrogen atom, a substituted or unsubstituted C ₁ to C ₃₀ alkyl group, a substituted or unsubstituted C ₁ to C ₃₀ alkoxy group, a substituted or unsubstituted C ₃ to C ₃₀ cycloalkyl group, a substituted or unsubstituted C ₂ ~C ₃₀ uial Kane group, a substituted or unsubstituted mono or a substituted or unsubstituted aryl group, a substituted or unsubstituted C ₆ ~C ₃₀ ring-di (C ₁ ~C ₃₀ alkyl) amino group, a substituted or unsubstituted mono- or di-ring - (C ₆ ~C ₃₀ aryl) amino group, a SF5, substituted or unsubstituted tree (C ₁ ~C ₃₀ of alkyl) silyl group, a substituted or unsubstituted ring Di (C _{1 to} C ₃₀ alkyl) (C _{6 to} C ₃₀ aryl) silyl, substituted or unsubstituted tri (C _{6 to} C ₃₀ aryl) silyl, cyano or halogen atom; R ₂₂₀ to R ₂₂₃ independently represent a hydrogen atom, a deuterium atom, a C _{1 to} C ₃₀ alkyl group optionally substituted by halogen, or a C _{6 to} C ₃₀ substituted or unsubstituted C _{1 to} C ₃₀ alkyl Lt; / RTI > R ₂₂₄ and R ₂₂₅ independently represent a hydrogen atom, a deuterium atom, a substituted or unsubstituted C ₁ to C ₃₀ alkyl group, a substituted or unsubstituted C ₆ to C ₃₀ aryl group, or a halogen atom, or R ₂₂₄ and R ₂₂₅ is connected by including the fused ring does not contain, or C ₃ ~C ₁₂ alkylene or C ₃ ~C ₁₂ of alkenylene to form an aliphatic ring, or a monocyclic or multi-fused ring; R ₂₂₆ is a substituted or unsubstituted C ₁ to C ₃₀ alkyl group, a substituted or unsubstituted C ₆ to C ₃₀ aryl group, a substituted or unsubstituted C ₅ to C ₃₀ heteroaryl group, or a halogen atom ; R ₂₂₇ to R ₂₂₉ independently represent a hydrogen atom, a deuterium atom, a substituted or unsubstituted C ₁ to C ₃₀ alkyl group, a substituted or unsubstituted C ₆ to C ₃₀ aryl group, or a halogen atom; Q is

,

or

And R ₂₃₁ to R ₂₄₂ are independently selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted C ₁ -C ₃₀ alkyl group, a substituted or unsubstituted C ₁ -C ₃₀ alkoxy group, a substituted or unsubstituted C ₆ aryl groups ~C _30, cyano furnace or a cycloalkyl group of the substituted or unsubstituted C ₅ ~C _30, alkenylene of an adjacent substituent via C ₃ ~C ₁₂ alkylene or C ₃ ~C ₁₂ of the spiro ring or May form a condensed ring, or may be connected to R ₂₀₇ or R ₂₀₈ by C ₃ -C ₁₂ alkylene or C ₃ -C ₁₂ alkenylene to form a saturated or unsaturated condensed ring.

The doping concentration is not particularly limited, but the content of the dopant is usually 0.01 to 15 parts by weight based on 100 parts by weight of the host. The thickness of the light emitting layer may be about 100 A to 1000 A, preferably 200 A to 600 A, When the thickness of the light emitting layer is less than 100 ANGSTROM, the light emission characteristics may be degraded. When the thickness of the light emitting layer is more than 1000 ANGSTROM, the driving voltage may increase.

When a luminescent compound is used together with a phosphorescent dopant in the luminescent layer, a method such as vacuum deposition, spin coating, casting, LB or the like is performed on the luminescent layer to prevent the triplet excitons or holes from diffusing into the electron transporting layer The hole blocking layer HBL can be formed. When the hole blocking layer is formed by a vacuum deposition method or a spin coating method, the conditions vary depending on the compound used, but are generally selected from substantially the same range of conditions as the formation of the hole injection layer. Known hole blocking materials that can be used include oxadiazole derivatives, triazole derivatives (TAZ), phenanthroline derivatives (BCP), and the like.

The thickness of the hole blocking layer may be about 50 Å to 1000 Å, preferably 100 Å to 300 Å. When the thickness of the hole blocking layer is less than 50 ANGSTROM, the hole blocking characteristics may be deteriorated. When the thickness of the hole blocking layer is more than 1000 ANGSTROM, the driving voltage may increase.

Next, an electron transport layer (ETL) is formed by various methods such as a vacuum evaporation method, a spin coating method, and a casting method.

In the case of forming the electron transporting layer by the vacuum deposition method and the spin coating method, the conditions vary depending on the compound used, but generally, the conditions are substantially the same as those for forming the hole injection layer. The electron transport layer material serves to stably transport electrons injected from an electron injection electrode, and quinoline derivatives, particularly known materials such as Alq3, TAZ, Balq, PBD and the like may be used.

The thickness of the electron transporting layer may be about 100 ANGSTROM to 1000 ANGSTROM, preferably 200 ANGSTROM to 500 ANGSTROM. When the thickness of the electron transporting layer is less than 100 ANGSTROM, the electron transporting property may be degraded. When the thickness of the electron transporting layer is more than 1000 ANGSTROM, the driving voltage may increase.

Further, an electron injection layer (EIL), which is a material having a function of facilitating the injection of electrons from the cathode, may be laminated on the electron transporting layer, which is not particularly limited. As the electron injection layer, any material known as an electron injection layer forming material such as LiF, NaCl, CsF, Li ₂ O, BaO, or the like can be used. The deposition conditions of the electron injection layer vary depending on the compound used, but are generally selected from substantially the same range of conditions as the formation of the hole injection layer. The thickness of the electron injection layer may be about 1 A to 100 A, preferably 5 A to 50 A. If the thickness of the electron injection layer is less than 1 A, the electron injection characteristics may be deteriorated. If the thickness of the electron injection layer exceeds 100 A, the driving voltage may increase.

Finally, the second electrode can be formed on the electron injection layer by a vacuum evaporation method, a sputtering method, or the like.

The second electrode may be used as a cathode. As the metal for forming the second electrode, a metal, an alloy, an electrically conductive compound having a low work function, or a mixture thereof may be used. Specific examples thereof include lithium (Li), magnesium (Mg), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium- .

Also, a transmissive cathode using ITO or IZO may be used to obtain a front light emitting element.

The organic electroluminescent compound according to another embodiment of the present invention is a carbazole-based compound represented by Formula F, more specifically, Compound 1 to 252 specifically exemplified in the first group (first group) . The details of the compounds are the same as those described for the organic foot and the device described above.

Hereinafter, Synthesis Examples and Examples of the present invention will be specifically described, but the present invention is not limited to the following Synthesis Examples and Examples. In the following synthesis examples, the intermediate compounds are indicated by adding the serial number to the final product number. For example, the compound 1 is represented by the compound [1], and the intermediate compound of the compound is represented by [1-1] or the like.

[Example]

Representative Synthesis Example 1. Synthesis of Compound 1

Preparation of intermediate compound [1-1]

109.3 g (380.65 mmol) of 5-bromo-1H-indazole and 253.76 mmol of (9-phenyl-9H-carbazol-3-yl) boronic acid were dissolved in 1 L of 1,4- Under reflux, 11.7 g (10.15 mmol) of tetrakis (triphenylphosphine) palladium, 10.52 g (761.28 mmol) of potassium carbonate and 100 mL of purified water were stirred under reflux for 24 hours. After completion of the reaction, distilled water and ethyl acetate were added at room temperature, and the organic layer was collected by layer separation. The organic layer was dried over anhydrous magnesium sulfate and filtered. The filtrate was distilled under reduced pressure to obtain 50.1 g (55%) of intermediate compound [1-1] as a white solid by column chromatography.

Preparation of compound [1]

5.1 g (16.69 mmol) of 4-bromo-2,6-diphenylpyridine, 0.79 g (4.17 mmol) of copper iodide, 1.17 g (20.86 mmol) of potassium hydroxide, 2.01 g (13.91 mmol) of 8-hydroxyquinoline and 100 mL of dimethylsulfoxide were placed, and the mixture was stirred at a temperature of 150 캜 in a nitrogen atmosphere. After completion of the reaction, methanol was added at room temperature, and the resulting solid was filtered. The filtered solid was washed with distilled water and methanol, and then recrystallized from dichloromethane and methanol to obtain 4.99 g (61%) of the desired compound [1] as a off-white solid.

Representative Synthesis Example 2. Synthesis of Compound 121

Preparation of intermediate compound [2-1]

(253.76 mmol) of 5-bromo-1H-indazole, 34 mL (304.51 mmol) of iodobenzene, 14.5 g (76.12 mmol) of copper iodide and 21.4 g (72%) of intermediate compound [2-1] as a white solid were obtained using 36.8 g (253.76 mmol) of 8-hydroxyquinoline, and dimethyl sulfoxide.

Preparation of intermediate compound [2-2]

(179.4 mmol) of intermediate compound [2-1], 36.4 mL (251.16 mmol) of 4,4,5,5-tetramethyl-1,3,2-dioxaborolane, tetrakis (triphenylphosphine) 6.2 g (5.38 mmol) of palladium and 1 L of 1,4-dioxane were placed, and the mixture was stirred in a nitrogen atmosphere. 176.4 ml (1255.8 mmol) of triethylamine was added dropwise to the reaction solution, and the mixture was heated to reflux and stirred. After completion of the reaction, distilled water and ethyl acetate were added at room temperature, and the organic layer was collected by layer separation. The organic layer was dried over anhydrous magnesium sulfate and filtered. The filtrate was distilled under reduced pressure to obtain 35 g (61%) of an intermediate compound [2-2] in the form of an oil by column chromatography.

Preparation of intermediate compound [2-3]

(109.31 mmol) of intermediate compound [2-2], 26.9 g (109.31 mmol) of 3-bromo-9H-carbazole and 3.7 g of tetrakis (triphenylphosphine) palladium 27.8 g (71%) of intermediate compound [2-3] as a yellow solid were obtained using 22.6 g (163.96 mmol) of potassium carbonate, and 1,4-dioxane.

Preparation of compound [121]

(11.12 mmol) of intermediate compound [2-3], 5.1 g (13.35 mmol) of 2- (3-bromophenyl) -4,6-diphenyl-1,3,5-triazine, sodium tertbutoxide 2.1 , 0.40 g (0.44 mmol) of tris (dibenzylideneacetone) dipalladium (0) and 100 mL of xylene, and the mixture was stirred under reflux in a nitrogen atmosphere. After completion of the reaction, distilled water and ethyl acetate were added at room temperature, and the organic layer was collected by layer separation. The organic layer was dried over anhydrous magnesium sulfate and filtered. The filtrate was distilled under reduced pressure, and dichloromethane and methanol were used to obtain 4.5 g (62%) of the desired compound [121] as a off-white solid.

Representative synthesis example 3. Synthesis of compound 138

Preparation of intermediate compound [3-1]

109 g (634.84 mmol) of 3-chloroperbenzoic acid was dissolved in 1.5 L of ethyl acetate, and then cooled to 0 ° C in a nitrogen atmosphere. At 0 < 0 > C, 50 g (423.22 mmol) of 4-azaindole was slowly added dropwise to the solid state. After completion of the reaction, the resulting solid was filtered at room temperature and washed with ethyl acetate to give 50.5 g (89%) of intermediate compound [3-1] as a pale purple solid.

Preparation of intermediate compound [3-2]

(372.74 mmol) of Intermediate Compound [3-1], 77.7 mL (372.74 mmol) of 1,1,1,3,3,3-hexamethyldisilazane and 1 L of toluene were stirred in a nitrogen atmosphere. 158.6 mL (931.85 mmol) of benzoyl chloride was slowly added dropwise to the reaction solution. After completion of the reaction, 500 mL of a 2M sodium hydrogencarbonate aqueous solution was added to the reaction solution and stirred. The organic layer was separated, washed with an aqueous solution of sodium chloride, dried over anhydrous magnesium sulfate and filtered. The filtrate was distilled off under reduced pressure, and dichloromethane and methanol were used to obtain 134.7 g (71%) of an intermediate compound [3-2] as a off-white solid.

Preparation of intermediate compound [3-3]

130 g (506.44 mmol) of the intermediate compound [3-2] were stirred in 1 L of methanol. The reaction was terminated by adding dropwise a 1 M aqueous solution of sodium hydroxide to the reaction solution. When the reaction was completed, the methanol was distilled off under reduced pressure, and ethyl acetate and distilled water were added thereto and stirred. The organic layer was separated, dried over anhydrous magnesium sulfate, and filtered. The filtrate was distilled under reduced pressure to obtain 57.9 g (75%) of intermediate compound [3-3] as a white solid by column chromatography.

Preparation of intermediate compound [3-4]

55 g (360.46 mmol) of intermediate compound [3-3], 124.1 g (432.55 mmol) of (9-phenyl-9H-carbazol- (70%) of intermediate compound [3-4] as a yellow solid was obtained using 8.3 g (7.20 mmol) of potassium carbonate, 74.7 g (540.69 mmol) of potassium carbonate and 1,4-dioxane .

Preparation of compound [138]

5 g (13.91 mmol) of the intermediate compound [3-4] and 6.4 g of 2- (3-bromophenyl) -4,6-diphenyl-1,3,5-triazine were obtained in the same manner as in the above- (16.69 mmol), copper iodide (0.79 g, 4.17 mmol), potassium hydroxide (1.17 g, 20.86 mmol), 8-hydroxyquinoline (2.0 g, 13.91 mmol) and dimethylsulfoxide ] Of 5.7 g (62%).

Representative synthesis example 4. Synthesis of compound 155

Preparation of intermediate compound [4-1]

20 g (131.07 mmol) of intermediate compound [3-2], 22 mL (196.61 mmol) of iodobenzene, 7.48 g (39.32 mmol) of copper iodide and 11.1 g (196.61 mmol) of potassium hydroxide were dissolved in the same manner as in the above- , 19 g (131.07 mmol) of 8-hydroxyquinoline and dimethyl sulfoxide was used to obtain 21.5 g (72%) of intermediate compound [4-1] as a white solid.

Preparation of intermediate compound [4-2]

21.6 g (91.83 mmol) of Intermediate Compound [4-1] and 18.6 mL (128.56 mmol) of 4,4,5,5-tetramethyl-1,3,2-dioxaborolane were obtained in the same manner as in Synthesis Example 2 17.6 g of intermediate compound [4-2] in oil state was obtained using 3.1 g (2.75 mmol) of tetrakis (triphenylphosphine) palladium, 70.7 mL (642.81 mmol) of triethylamine and 1,4- (60%).

Preparation of intermediate compound [4-3]

(53.09 mmol) of intermediate compound [4-2], 10.8 g (44.24 mmol) of 3-bromo-9H-carbazole and 1.1 g of tetrakis (triphenylphosphine) palladium 0.8 g, 0.88 mmol), potassium carbonate (9.1 g, 66.36 mmol), and 1,4-dioxane was used to obtain 11.1 g (70%) of intermediate compound [4-3] as a yellow solid.

Preparation of compound [155]

4 g (11.12 mmol) of the intermediate compound [4-3] and 5.1 g of 2- (3-bromophenyl) -4,6-diphenyl-1,3,5-triazine in the same manner as in the above- 0.33 g (0.44 mmol) of tris (dibenzylideneacetone) dipalladium (0) and 0.35 g (0.44 mmol) of tributylphosphine, To give 4.4 g (61%) of the desired compound as an off-white solid.

Compounds 1 to 252 were synthesized according to the methods of Representative Synthesis Examples 1 to 4 described above. Nuclear magnetic resonance spectroscopy (NMR) and mass spectrometry (MS) 2 group (group)].

[Second group (group)]

Comparative Example 1. Preparation of Comparative Sample 1

A compound represented by the following formula (a) is used as a phosphorescent green host, and a compound represented by the following formula (c) is used as a phosphorescent green dopant to prepare a 4,4 ', 4 "-tris (N-naphthalen- (N-phenylamino) -triphenylamine (hereinafter abbreviated as '2-TNATA') was used as a hole injection layer material and N, N'-di (naphthalen- 2-TNATA (80 nm) /? -NPD (30 nm) / Compound (2) was prepared by using benzidine (hereinafter abbreviated as? -NPD) as a hole transport layer material. a + compound c (30 nm) / Alq (30 nm) / LiF (0.5 nm) / Al (60 nm).

An anode was prepared by cutting Corning's 15 Ω / cm ² (1000 Å) ITO glass substrate to a size of 50 mm × 50 mm × 0.7 mm, ultrasonically cleaning it in acetone, isopropyl alcohol and pure water for 15 minutes each, Min for UV ozone cleaning. 2-TNATA was vacuum deposited on the substrate to form a hole injection layer having a thickness of 80 nm. On top of the hole injection layer, α-NPD was vacuum deposited to form a hole transport layer having a thickness of 30 nm. A compound represented by the formula a and a compound c represented by the formula c (doping ratio: 10%) were vacuum deposited on the hole transport layer to form a light emitting layer with a thickness of 30 nm. Then, an Alq ₃ compound was vacuum deposited on the light emitting layer to a thickness of 30 nm to form an electron transporting layer. LiF 0.5 nm (electron injecting layer) and Al 60 nm (cathode) were sequentially vacuum-deposited on the electron transporting layer to form an organic light emitting device as shown in the third table group (3). This is referred to as Comparative Sample 1.

Comparative Example 2. Production of Comparative Sample 2

2-TNATA is used as a hole injection layer material, and the compound represented by the following formula (b) is used as a phosphorescent green host, the compound c represented by the following formula (c) is used as a phosphorescent green dopant, (30 nm) / compound (30 nm) / Alq ₃ (30 nm) / LiF (30 nm) / compound (30 nm) / ITO / 2-TNATA 0.5 nm) / Al (60 nm).

An anode was prepared by cutting Corning's 15 Ω / cm ² (1000 Å) ITO glass substrate to a size of 50 mm × 50 mm × 0.7 mm, ultrasonically cleaning it in acetone, isopropyl alcohol and pure water for 15 minutes each, Min for UV ozone cleaning. 2-TNATA was vacuum deposited on the substrate to form a hole injection layer having a thickness of 80 nm. On top of the hole injection layer, α-NPD was vacuum deposited to form a hole transport layer having a thickness of 30 nm. A compound represented by the formula (a) and a compound represented by the formula c (doping ratio: 10%) were vacuum deposited on the hole transport layer to form a light emitting layer with a thickness of 30 nm. Then, an Alq ₃ compound was vacuum deposited on the light emitting layer to a thickness of 30 nm to form an electron transporting layer. LiF 0.5 nm (electron injecting layer) and Al 60 nm (cathode) were sequentially vacuum-deposited on the electron transporting layer to form an organic light emitting device as shown in the third table group (3). This is referred to as Comparative Sample 2.

Comparative Example 3. Production of Comparative Sample 3

A compound represented by the following formula (a) is used as a host, a compound represented by the following formula (d) is used as a dopant, 2-TNATA is used as a hole injecting layer material and? -NPD is used as a hole transporting layer material (30 nm) / Alq3 (30 nm) / LiF (0.5 nm) / Al (30 nm) / compound a + compound d (30 nm) / ITO / 2-TNATA (60 nm).

An anode was prepared by cutting Corning's 15 Ω / cm ² (1000 Å) ITO glass substrate to a size of 50 mm × 50 mm × 0.7 mm, ultrasonically cleaning it in acetone, isopropyl alcohol and pure water for 15 minutes each, UV ozone cleaning was used. 2-TANATA was vacuum-deposited on the substrate to form a hole injection layer having a thickness of 80 nm. On top of the hole injection layer, α-NPD was vacuum deposited to form a hole transport layer having a thickness of 30 nm. Compound (a) represented by Formula (a) and Compound d (10% doped) represented by Formula (d) were vacuum deposited on the hole transport layer to form a 30 nm thick light emitting layer. Then, an Alq3 compound was vacuum deposited on the light emitting layer to a thickness of 30 nm to form an electron transporting layer. LiF 0.5 nm (electron injecting layer) and Al 60 nm (cathode) were sequentially vacuum-deposited on the electron transporting layer to form an organic light emitting device as shown in the third table group (3). This is referred to as Comparative Sample 3.

Examples 1 to 252. Sample preparation

In Comparative Example 1, the phosphorescent host compound a was used instead of the phosphorescent host compound a in the synthesis examples. (30 nm) / [phosphorescent green host compound 1 to 252 + compound c (10%)] (30 nm) /? -NPD An organic light emitting device having a structure of Alq ₃ (30 nm) / LiF (0.5 nm) / Al (60 nm) was fabricated. These are referred to as Samples 1 to 252, respectively.

Examples 253 to 283. Sample preparation

In the above Comparative Example 3, instead of the compound a as the phosphorescent host compound, the compounds represented by the above formula (13) were used as the host compound in the light emitting layer, respectively. (30 nm) / Alq3 (30 nm) / LiF (0.5 nm) / [NPD (30 nm) / nm) / Al (60 nm). These are referred to as Samples 253 to 283, respectively.

[Experimental Example] Characteristic evaluation

Experimental Example 1: Evaluation of luminescence characteristics

1) Evaluation of luminescence characteristics of Samples 1 to 252

The emission luminance, the luminous efficiency, and the emission peak were evaluated using Keithley source meter "2400" and KONIKA MINOLTA "CS-2000" for Comparative Samples 1 and 2 and Samples 1 to 252 produced in the above Comparative Examples and Examples, respectively , And the results are shown in the following [third group (group)]. The samples showed green emission peak values in the 511-517 nm range.

[Group 3]

Samples 1 to 252 exhibited improved luminescence characteristics as compared to Comparative Samples 1 and 2, as confirmed from the [third set of groups (group)].

2) Evaluation of luminescence characteristics of Samples 253 to 283

The emission luminance, the luminous efficiency, and the emission peak were evaluated using Keithley SMU 235 and PR650 for the comparative sample 3 and the samples 253 to 283 prepared in the comparative example and the example, Group)]. The samples showed red emission peak values in the 610-616 nm range.

[Group 4]

Samples 327 to 360 exhibited improved luminescence properties as compared to Comparative Sample 3, as confirmed from [fourth set of group (s)] above.

Experimental Example 2: Evaluation of Life Characteristic

1) Evaluation of life characteristics of Samples 1 to 252

For each of Comparative Samples 1 and 2 and Samples 1 to 252 produced in the above Comparative Examples and Examples, the time at which the lifetime reaches 97% based on 3000 nits was measured using an LTS-1004AC life measuring device manufactured by ENC Technologies, Inc. Respectively. The results are shown below in the fifth group (group).

[Fifth group (group)]

Samples 1 to 252 exhibited improved lifespan characteristics as compared to Comparative Samples 1 and 2, as confirmed from [fifth set of group (s)].

2) Evaluation of life characteristics of samples 253 to 283

For the Comparative Sample 3 and the samples 253, 258, 260, 265, 277, and 282 prepared in the above Comparative Examples and Examples, the intensity of luminescence was measured in a DC mode using a LTS- The lifetime was evaluated by a time which decreased to 70% of the initial value. The results are shown below in the sixth group (group).

[Group 6]

Samples 253, 258, 260, 265, 277, and 282 showed improved lifespan characteristics as compared to Comparative Sample 3, as confirmed from [sixth set of group (s)

Claims (10)

A carbazole-based organic light-emitting compound represented by the following formula (F):
[Chemical Formula F]

In Formula (F) above,
Wherein R ₁ , R ₂ and R ₄ are hydrogen atoms, and R ₃ is

or

ego,
X is a single bonding line, or -O-, -S-, -NH-, -N- phenyl, -Si (C ₁ -C _{6 alkyl) 2 -, - CH 2 -} , - C (C 1 -C 6 Alkyl) ₂ -;
Wherein said LP < _{1 >} is selected from the group:

Wherein Het is selected from the group consisting of mono (C ₆ -C ₄₀ aryl) amine, di (C ₆ -C ₄₀ aryl) amine and 1 to 4 heteroatoms selected from N, O, S, P, C ₃ -C ₄₀ heteroaryl and C ₃ -C ₄₀ heterocycloalkyl of the double or triple ring,
A is selected from the group consisting of C ₁ -C ₄₀ alkane, C ₅ -C ₄₀ cycloalkane, C ₂ -C ₄₀ alkene, C ₂ -C ₄₀ alkyne, C ₆ -C ₄₀ aryl, tri (C ₁ -C ₄₀ alkyl) (C ₁ -C ₄₀ alkyl) silane, tri (C ₆ -C ₄₀ aryl) silane, and tetra (C ₆ -C ₄₀ aryl) silane,
R ^a is C ₁ -C ₄₀ alkyl, C ₆ -C ₄₀ aryl group, -O- (C ₆ -C ₄₀ aryl), -S- (C ₆ -C ₄₀ aryl), - (C ₆ -C ₄₀ aryl _{alkylene) P (O) (C 6} -C 40 _{aryl) 2, -NH (C 6 -C} 40 aryl), -N (C ₆ -C _{40 aryl) 2, -Si (C 6 -C} 40 aryl) ₃ Or a C ₃ -C ₄₀ heteroaryl group containing 1 to 4 nitrogen atoms (N), m is an integer of 0 to 4 as the number of the substituents R ^a ;
P ₂ is

ego;
In the definition of P ₂ above, Het 1 is a mono (C ₆ -C ₄₀ aryl) amine, di (C ₆ -C ₄₀ aryl) amine and 1 to 4 heteroatoms selected from N, O, S, P, C ₃ -C ₄₀ heteroaryl and C ₃ -C ₄₀ heterocycloalkyl, and is a mono- or di-trico radical derived from the group consisting of mono-, di- or tri-cyclic C ₃ -C ₄₀ heteroaryl and C ₃ -C ₄₀ heterocycloalkyl,
In the definition of P < ₂ >, A, R < ^a > and m are as defined above. The method according to claim 1,
Wherein X is a single bonding line, or _{-C (CH 3) (CH 3} ) - of the organic electroluminescent compounds according to claim. delete delete delete delete The method according to claim 1,
The A may be at least one member selected from the group consisting of benzene, biphenyl, bithiophene, naphthalene, 1- (naphthalen-5-yl) naphthalene, 1- (1-phenylnaphthalen-4-yl) naphthalene, fluorene, spirobifluorene, (Biphenyl) silane, and tetraphenylsilane. ≪ Desc / Clms Page number 18 > The method according to claim 1,
Wherein A is an aliphatic mono or divalent radical derived from the group consisting of methane, ethane, ethene, ethyne, cyclohexane, piperidine, and piperazine. The method according to claim 1,
Wherein the Het is selected from the group consisting of phenylamine, diphenylamine, furan, thiophene, pyrrole, thiazole, thiadiazole, oxazole, oxadiazole, imidazole, pyrazole, triazole, pyridine, pyrimidine, pyrazine, pyridazine, And examples thereof include triazine, tetrazine, benzothiophene, indole, indolizine, benzoimidazole, benzoxazole, benzothiazole, dihydroindazole, imidazopyridine, pyrrolopyridine, imidazolopyridine, pyrazolopyridine, Pyridopyrimidine, pyrazinopyrazine, acridine, 9,10-dihydro-9,10-dimethylacridine, phenanthridine, isoquinoline, quinoxaline, quinazoline, phthalazine, naphthyridine, Pyridine, pyridine, pyridine, pyridine, pyridine, pyridine, pyridine, pyridine, pyridine,

(Wherein, X ₁ is -O-, -S-, -NH-, -N- phenyl, -Si (C ₁ -C _{6 alkyl) 2 -, - CH 2 -} , - C (C 1 -C 6 alkyl ) ₂ -, -CH ₂ CH ₂ -, or -CH = CH-,

The

,

,

,

Wherein R < 1 > is a monovalent or divalent radical derived from the group consisting of R < 1 > The method according to claim 1,
Wherein R is ^a tert- butyl group, a phenyl group, a biphenyl group, -O- phenyl, -S- _{phenyl, -C 6 H 4 -P (O} ) ( phenyl) _2, -Si (phenyl) _3, -Si (by phenyl) (phenyl) _2, -NH (phenyl), -N (phenyl) _2, pyridinyl, pyrazolyl group, and the triazine is selected from the group, a wherein m is an integer of 0 to 4 as the number of the R ^a substituent possess Wherein the organic light-emitting compound is a compound represented by formula