KR101513870B1 - An aromatic heterocyclic compound an organic light emitting diode comprising an organic layer comprising the same and an method for preparing the organic light emitting diode - Google Patents

Abstract

There is provided an aromatic heterocyclic compound represented by the following formula (1), an organic light emitting device having the same, a method of manufacturing the organic light emitting device,

≪ Formula 1 >

The description of Formula 1 refers to the detailed description of the invention.

Organic light emitting device

Description

An aromatic heterocyclic compound, an organic light emitting device having an organic film containing the organic heterocyclic compound, and an organic light emitting device comprising the organic heterocyclic compound, an organic light emitting diode }

An organic light emitting device having an aromatic heterocyclic compound, an organic film containing the organic heterocyclic compound, and a method of manufacturing the organic light emitting device, and more particularly, to a method of manufacturing the organic light emitting device, And a long life, an organic light emitting device having an organic film containing the aromatic heterocyclic compound, and a method of manufacturing the organic light emitting device.

Organic light emitting diodes (OLEDs) have been studied in terms of excellent luminance, driving voltage, and response speed characteristics and being able to have multiple colors.

The organic light emitting device generally has a stack structure of an anode / organic light emitting layer / cathode, and includes an anode / a hole injecting layer / a hole transporting layer / a light emitting layer / an electron transporting layer / an electron injecting layer / a cathode or an anode / a hole injecting layer / a hole transporting layer / Electron transport layer / electron injection layer / cathode, and the like.

The materials used for the organic light emitting device can be divided into a vacuum vapor deposition material and a solution coating material according to a manufacturing method of an organic film. In the case of using an organic light emitting device using a vacuum deposition method using a vacuum vapor deposition material, the use of a vacuum system and the use of a shadow mask for manufacturing a pixel for a color display are required. On the other hand, in the case of using an organic light emitting device using a solution coating material such as inkjet printing, screen printing, or spin coating, the manufacturing cost can be lower than in the case of using a vacuum deposition method relatively.

Therefore, it is required to develop a compound capable of forming an organic film having excellent heat stability and luminescence properties, irrespective of the organic film formation method, as a compound usable in an organic light emitting device.

It is desired to develop a compound capable of forming an organic film having excellent heat stability and light emission characteristics regardless of the organic film formation method as a compound which can be used for an organic light emitting device.

There is provided an aromatic heterocyclic compound represented by the following Formula 1:

≪ Formula 1 >

In Formula 1,

R ₁ to R ₉ independently represent hydrogen, halogen, cyano group, nitro group, hydroxyl group, substituted or unsubstituted C ₁ -C ₂₀ alkyl group, substituted or unsubstituted C ₂ -C ₂₀ alkenyl group, substituted or unsubstituted C ₂ -C ₂₀ alkynyl group, a substituted or unsubstituted C ₅ -C ₂₀ cyclo alkyl group, a substituted or unsubstituted C ₅ -C ₂₀ cyclo alkenyl group, a substituted or unsubstituted C ₅ -C ₂₀ aryl A substituted or unsubstituted C ₂ -C ₃₀ heteroaryl group, or -N (Z ₁ ) (Z ₂ ), Z ₁ and Z ₂ are each independently of the other hydrogen, A substituted or unsubstituted C ₁ -C ₂₀ alkyl group or a substituted or unsubstituted C ₅ -C ₂₀ aryl group;

R ₁₀ to R ₁₂ independently represent hydrogen, halogen, cyano, nitro, hydroxyl, substituted or unsubstituted C ₁ -C ₂₀ alkyl, substituted or unsubstituted C ₂ -C ₂₀ alkenyl, substituted or unsubstituted C ₂ -C ₂₀ alkynyl group, a substituted or unsubstituted C ₅ -C ₂₀ cyclo alkyl group, a substituted or unsubstituted C ₅ -C ₂₀ cyclo alkenyl group, a substituted or unsubstituted C ₅ -C ₂₀ aryl A substituted or unsubstituted C ₂ -C ₂₀ heteroaryl group, a group represented by -N (Z ₁ ) (Z ₂ ), or a group represented by -Q ₁ -Q ₂ , and Z ₁ and Z ₂ Independently of one another, hydrogen, a substituted or unsubstituted C ₁ -C ₂₀ alkyl group or a substituted or unsubstituted C ₅ -C ₂₀ aryl group, Q ₁ is a C ₅ -C ₂₀ arylene group or a C ₂ -C ₂₀ And Q ₂ is a substituted or unsubstituted C ₅ -C ₂₀ aryl group or a substituted or unsubstituted C ₂ -C ₂₀ heteroaryl group;

a, b and c are 0, 1 or 2;

X is CY ₁ or N, and Y ₁ is hydrogen, a substituted or unsubstituted C ₁ -C ₂₀ alkyl group or a substituted or unsubstituted C ₁ -C ₂₀ alkoxy group.

Further, there is provided an organic light emitting device comprising a first electrode, a second electrode, and an organic film containing an aromatic heterocyclic compound represented by the above-mentioned formula (1) between the first electrode and the second electrode.

Further, forming a first electrode on the substrate; Forming an organic film comprising an aromatic heterocyclic compound represented by Formula 1 above on the first electrode; And forming a second electrode on the organic layer.

The aromatic heterocyclic compound represented by Formula 1 may be applied to an organic light emitting device to provide excellent electrical characteristics.

Among the aromatic heterocyclic compounds represented by the following formula (1)

≪ Formula 1 >

R ₁₀ to R ₁₂ independently represent hydrogen, halogen, cyano, nitro, hydroxyl, substituted or unsubstituted C ₁ -C ₂₀ alkyl, substituted or unsubstituted C ₂ -C ₂₀ alkenyl, substituted or unsubstituted C ₂ -C ₂₀ alkynyl group, a substituted or unsubstituted C ₅ -C ₂₀ cyclo alkyl group, a substituted or unsubstituted C ₅ -C ₂₀ cyclo alkenyl group, a substituted or unsubstituted C ₅ -C ₂₀ aryl A substituted or unsubstituted C ₂ -C ₂₀ heteroaryl group, a group represented by -N (Z ₁ ) (Z ₂ ), or a group represented by -Q ₁ -Q ₂ . Wherein Z ₁ and Z ₂ are independently of each other hydrogen, a substituted or unsubstituted C ₁ -C ₂₀ alkyl group or a substituted or unsubstituted C ₅ -C ₂₀ aryl group, Q ₁ is C ₅ -C ₂₀ arylene group or a C ₂ -C ₂₀ heteroarylene group, and Q ₂ may be a substituted or unsubstituted C ₅ -C ₂₀ aryl group or a substituted or unsubstituted C ₂ -C ₂₀ heteroaryl group.

R ₁₀ to R ₁₂ as described above may be independently of each other, and may be located at the same position as in the following formula (1a):

<Formula 1a>

Specifically, R ₁₀ to R ₁₂ in the formula (1) are, independently of each other, hydrogen, a substituted or unsubstituted C ₁ -C ₂₀ alkyl group, a substituted or unsubstituted C ₅ -C ₂₀ aryl group, a substituted or unsubstituted C ₂ -C ₂₀ heteroaryl group, or a -Q ₁ group is represented by -Q _2, wherein Q ₁ is C ₅ -C ₂₀ arylene group, and wherein Q ₂ is a substituted or unsubstituted C ₅ -C ₂₀ aryl group Or a substituted or unsubstituted C ₂ -C ₂₀ heteroaryl group. More specifically, R ₁₀ to R ₁₂ in the general formula (1) are, independently from each other, hydrogen, a substituted or unsubstituted C ₁ -C ₁₀ alkyl group, a substituted or unsubstituted C ₅ -C ₁₄ aryl group, C ₂ -C ₁₄ heteroaryl group or a group represented by -Q ₁ -Q ₂ , Q ₁ is a C ₅ -C ₁₄ arylene group, and Q ₂ is a substituted or unsubstituted C ₅ -C ₁₄ aryl Or a substituted or unsubstituted C ₂ -C ₁₄ heteroaryl group.

Examples of the substituent for R ₁₀ to R ₁₂ as described above include a halogen atom, a hydroxy group, a nitro group, a cyano group, an amino group, an amidino group, a hydrazine, a hydrazone, a carboxyl group or a salt thereof, Or a salt thereof, but is not limited to, a C ₁ -C ₁₀ alkyl group, a C ₁ -C ₁₀ alkoxy group, a C ₆ -C ₃₀ aryl group, or a C ₂ -C ₂₀ heteroaryl group. Specifically, the substituent of R ₁₀ to R ₁₂ may be a C ₁ -C ₁₀ alkyl group or a C ₆ -C ₃₀ aryl group.

In Formula 1, a, b, and c may independently be 0, 1, or 2. When a, b and c are two or more, a plurality of R ₁₀ to R _12, etc. may be different from each other or the same.

More specifically, R ₁₀ to R ₁₂ in the formula (1) may be any one of the following formulas (2a) to (2o), but is not limited thereto:

In Formula 1, X is CY ₁ or N, and Y ₁ may be hydrogen, a substituted or unsubstituted C ₁ -C ₂₀ alkyl group, or a substituted or unsubstituted C ₁ -C ₂₀ alkoxy group.

As the substituent of Y ₁ described above, for example, a halogen atom, a hydroxy group, a nitro group, a cyano group, an amino group, an amidino group, a hydrazine, a hydrazone, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, , Or a C ₁ -C ₁₀ alkyl group, a C ₁ -C ₁₀ alkoxy group, a C ₆ -C ₃₀ aryl group, or a C ₂ -C ₂₀ heteroaryl group, but is not limited thereto. Specifically, the substituent of Y ₁ may be a C ₁ -C ₁₀ alkyl group or a C ₆ -C ₃₀ aryl group.

More specifically, Y ₁ may be a substituted or unsubstituted C ₁ -C ₁₀ alkyl group or a substituted or unsubstituted C ₁ -C ₁₀ alkoxy group.

According to one embodiment of the aromatic heterocyclic compound represented by Formula 1, X may be CH or N, but is not limited thereto.

Wherein R ₁ to R ₉ independently represent hydrogen, halogen, cyano group, nitro group, hydroxyl group, substituted or unsubstituted C ₁ -C ₂₀ alkyl group, substituted or unsubstituted C ₂ -C ₂₀ alkenyl group, a substituted or unsubstituted C ₂ -C ₂₀ alkynyl group, a substituted or unsubstituted C ₅ -C ₂₀ cyclo alkyl group, a substituted or unsubstituted C ₅ -C ₂₀ cyclo alkenyl group, a substituted or unsubstituted C _A C ₅ -C ₂₀ aryl group, a substituted or unsubstituted C ₂ -C ₃₀ heteroaryl group, or -N (Z ₁ ) (Z ₂ ). Here, Z ₁ and Z ₂ may be, independently of each other, hydrogen, a substituted or unsubstituted C ₁ -C ₂₀ alkyl group or a substituted or unsubstituted C ₅ -C ₂₀ aryl group.

Examples of the substituent of R ₁ to R ₉ as described above include a halogen atom, a hydroxy group, a nitro group, a cyano group, an amino group, an amidino group, a hydrazine, a hydrazone, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, Or a salt thereof, but is not limited to, a C ₁ -C ₁₀ alkyl group, a C ₁ -C ₁₀ alkoxy group, a C ₆ -C ₃₀ aryl group, or a C ₂ -C ₂₀ heteroaryl group. Preferably, the substituent of R ₁ to R ₉ may be a C ₁ -C ₁₀ alkyl group or a C ₆ -C ₃₀ aryl group.

Specifically, R ₁ to R ₉ independently of each other may be hydrogen, a substituted or unsubstituted C ₅ -C ₂₀ aryl group, or a substituted or unsubstituted C ₂ -C ₃₀ heteroaryl group. In particular, when R ₁ to R ₉ are, independently from each other, hydrogen, a substituted or unsubstituted C ₅ -C ₂₀ aryl group or a substituted or unsubstituted C ₂ -C ₃₀ heteroaryl group, The film forming ability of an organic film containing an aromatic heterocyclic compound can be improved, and stability can be increased. More specifically, R ₁ to R ₉ may be, independently of each other, hydrogen, a substituted or unsubstituted C ₅ -C ₁₄ aryl group or a substituted or unsubstituted C ₂ -C ₁₄ heteroaryl group.

More specifically, R ₁ to R ₄ and R ₆ to R ₉ are hydrogen and R ₅ is independently of each other hydrogen, a substituted or unsubstituted C ₅ -C ₂₀ aryl group or a substituted or unsubstituted C ₂ -C ₃₀ heteroaryl date can, but is not limited to this.

Specifically, R ₁ to R ₉ independently of each other may be hydrogen or any of the following formulas (3a) to (3i), but are not limited thereto:

Preferably, the aromatic heterocyclic compound may be represented by the following Formula 1b:

&Lt; EMI ID =

The definition of R ₁₀ to R ₁₂ and X in the above formula (1b) is as described above.

In the above formula (1b), Q ₃ may be hydrogen or an unsubstituted C ₅ -C ₂₀ aryl group, preferably hydrogen or an unsubstituted C ₅ -C ₁₄ aryl group.

In the present specification, specific examples of the unsubstituted C ₁ -C ₂₀ alkyl group include methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, iso-amyl, hexyl and the like. It is a halogen atom, a hydroxy group, a nitro group, a cyano group, an amino group, an amidino group, hydrazine, hydrazone, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, phosphoric acid or a salt thereof, or a C ₁ -C ₃₀ alkyl, C ₁ -C ₃₀ alkoxy group, C ₁ -C ₃₀ alkenyl, C ₁ -C ₃₀ alkynyl, C ₆ -C ₃₀ aryl may be substituted with a group, or a C ₂ -C ₂₀ heteroaryl group.

In the present specification, specific examples of the unsubstituted C ₁ -C ₂₀ alkoxy group include methoxy, ethoxy, phenyloxy, cyclohexyloxy, naphthyloxy, isopropyloxy, diphenyloxy and the like. At least one hydrogen atom in the alkoxy group may be substituted with the same substituent as in the case of the alkyl group described above.

In the present specification, an unsubstituted C ₂ -C ₂₀ alkenyl group means that the alkyl group as defined above contains a carbon double bond at the middle or the far end. Examples include ethylene, propylene, butylene, hexylene and the like. At least one hydrogen atom in these alkenyl groups may be substituted with the same substituent as in the case of the above-mentioned alkyl group.

In the present specification, the unsubstituted C ₂ -C ₂₀ alkynyl group means that a triple bond is contained at the middle or the far end of the alkyl group as defined above, and at least one of the hydrogen atoms is the above-mentioned alkyl group May be substituted with the same substituent as the case. Examples thereof include acetylene, propylenyl, phenylacetylene, naphthylacetylene, isopropylacetylene, t-butylacetylene, diphenylacetylene and the like.

In the present specification, an unsubstituted C ₅ -C ₂₀ aryl group means a carbocyclic aromatic system having 5 to 20 carbon atoms, including at least one aromatic ring. When two or more rings are included, they may be fused with each other, And the like. At least one hydrogen atom of the aryl group may be substituted with the same substituent as the alkyl group described above.

In the present specification, examples of the substituted or unsubstituted C ₅ -C ₂₀ aryl group include phenyl group, C ₁ -C ₁₀ alkylphenyl group (for example, ethylphenyl group), halophenyl group (for example, o-, m- and with p- fluorophenyl group, dichlorophenyl group), a cyano group, a dicyanomethylene group, a trifluoromethoxy group, a biphenyl group, a halo-biphenyl group, a cyanobiphenyl group, a C ₁ -C ₁₀ biphenyl group, C ₁ -C ₁₀ alkoxy non (N, N'-dimethyl) phenyl group, o-, m-, and p-tolyl group, o-, m- and p-cumenyl group, mesityl group, phenoxyphenyl group, (For example, fluoronaphthyl group), a C ₁ -C ₁₀ alkylnaphthyl group (for example, a group represented by the following formula ( ₁ )), an aminophenyl group, (For example, methyl naphthyl group), C ₁ -C ₁₀ alkoxynaphthyl group (for example, methoxynaphthyl group), cyanonaphthyl group, anthracenyl group and azrenyl group. It is to be understood that these may be substituted like the substituent for the alkyl group.

In the present specification, the unsubstituted C ₅ -C ₂₀ arylene group is a divalent linking group having a structure similar to the aryl group, examples of which include a phenylene group and a naphthylene group, but are not limited thereto. At least one hydrogen atom of the arylene group may be substituted with the same substituent as the alkyl group described above.

As used herein, an unsubstituted C ₂ -C ₂₀ heteroaryl group means a system consisting of one or more aromatic rings containing one or more heteroatoms selected from N, O, P or S and the remaining ring atoms C, The above aromatic rings may be fused to each other, or may be connected to each other through a single bond or the like. At least one hydrogen atom of the heteroaryl group may be substituted with a substituent similar to that of the alkyl group described above.

In the present specification, examples of the unsubstituted C ₂ -C ₂₀ heteroaryl group include a pyrazolyl group, an imidazolyl group, an oxazolyl group, a thiazolyl group, a triazolyl group, a tetrazolyl group, an oxadiazolyl group, A pyridazinyl group, a pyrimidinyl group, a triazinyl group, a carbazolyl group, an indolyl group, a quinolinyl group, an isoquinolinyl group and the like. It is to be understood that these substituents may be substituted with the substituents of the alkyl group.

In the present specification, an unsubstituted C ₅ -C ₂₀ cycloalkyl group refers to an alkyl group having a ring system, and an unsubstituted C ₅ -C ₂₀ cycloalkenyl group refers to an alkenyl group having a ring system. At least one of the hydrogen atoms of the cycloalkyl group and the cycloalkenyl group may be substituted with the same substituent as the alkyl group described above.

One embodiment of the aromatic heterocyclic compound represented by formula (1) according to the present invention may be one of the following compounds 1 to 17, but is not limited thereto:

&Lt; Compound 1 > < Compound 2 >

&Lt; Compound 3 > < Compound 4 >

&Lt; Compound 5 > < Compound 6 >

&Lt; Compound 7 > < Compound 8 >

&Lt; Compound 9 > < Compound 10 &

&Lt; Compound 11 > < Compound 12 >

&Lt; Compound 13 > < Compound 14 >

&Lt; Compound 15 > < Compound 16 >

<Compound 17>

The aromatic heterocyclic compound of the present invention represented by the above formula (1) can be synthesized by a conventional organic synthesis method.

The antistatic heterocyclic compound represented by the general formula (1) as described above may be included in the organic layer of the organic light emitting device. Accordingly, there is provided an organic light emitting device comprising a first electrode, a second electrode, and an organic film provided between the first electrode and the second electrode and including an aromatic heterocyclic compound represented by the above-mentioned formula (1).

Preferably, the organic film may be a light emitting layer or an electron transporting layer.

An organic film containing an aromatic heterocyclic compound represented by the general formula (1) as described above can be formed by various known methods. For example, a solution coating method such as vacuum evaporation or spin coating, inkjet printing, screen printing, casting, LB, spray printing and the like can be used. Further, an organic film containing an aromatic heterocyclic compound represented by the above formula (1) is formed on the donor film by the vacuum deposition method or the solution coating method as described above, and then thermally transferred to the substrate on which the first electrode or the like is formed May be used. Among them, the aromatic heterocyclic compound represented by Formula 1 can form a stable organic film having excellent solubility and thermal stability, unlike the case of the conventional organic light emitting device in which the stability of the organic film is poor when the solution coating method is used , A low driving voltage, a high efficiency and a high luminance can be obtained.

The organic light emitting device may further include at least one layer selected from the group consisting of a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer, an electron transport layer, and an electron injection layer between the first electrode and the second electrode. More specifically, an embodiment of the organic light emitting device is described with reference to FIGS. 1A, 1B, and 1C. The organic electroluminescent device of FIG. 1A has a structure of a first electrode / a hole transporting layer / a light emitting layer / an electron transporting layer / an electron injecting layer / a second electrode, and the organic light emitting device of FIG. 1B includes a first electrode / a hole injecting layer / Emitting layer / electron transporting layer / electron injecting layer / second electrode. 1C has a structure of a first electrode / a hole injection layer / a hole transport layer / a light emitting layer / a hole blocking layer / an electron transport layer / an electron injection layer / a second electrode. At this time, at least one of the light emitting layer, the hole injecting layer, the hole transporting layer, the hole blocking layer or the electron transporting layer may include the aromatic heterocyclic compound represented by the above formula (1).

Hereinafter, a method of manufacturing an organic light emitting diode according to an embodiment of the present invention will be described with reference to the organic light emitting diode shown in FIG. 1C.

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 (SnO2), zinc oxide (ZnO) or the like is used which is transparent and excellent in conductivity.

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 vacuum degree of 10 ^-8 to 10 ^-3 torr, and a deposition rate of 0.01 to 100 Å / sec.

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

As the hole injection layer material, a known hole injection material may be used. For example, m-MTDATA [4,4 ', 4 "-tris (3-methylphenylphenylamino) triphenylamine], NPB (N, N'-di (1-naphthyl) -N, N'-diphenylbenzidine PEDOT / PSS (Poly (N, N'-di (1-naphthyl) -N, N'-diphenylbenzidine), TDATA, 2T-NATA, Pani / DBSA 3,4-ethylenedioxythiophene / poly (4-styrenesulfonate) / poly (4-styrene sulfonate) / Pani / CSA (polyaniline / camphor sulfonic acid) Or PANI / PSS (polyaniline) / poly (4-styrenesulfonate): polyaniline) / poly (4-styrenesulfonate).

The thickness of the hole injection layer may be about 100 Å to 10000 Å, preferably 100 Å to 1000 Å. When the thickness of the hole injection layer satisfies the above-described range, satisfactory hole injection characteristics can be obtained without substantially lowering the driving voltage.

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.

As the hole transport layer material, a known hole transport material can be used. Carbazole derivatives such as N, N'-bis (3-methylphenyl) -N, N'-diphenyl- [1,1-biphenyl] -4,4'- Amine derivative having an aromatic condensed ring such as diamine (TPD), N, N'-di (naphthalene-1-yl) -N, N'-diphenylbenzidine (? -NPD) Known hole transporting materials such as triphenylamine-based materials such as tris (N-carbazolyl) triphenylamine (4,4 ', 4 "-tris (N-carbazolyl) triphenylamine)

The thickness of the hole transporting layer may be about 50 Å to 1000 Å, preferably 100 Å to 800 Å. When the thickness of the hole transporting layer satisfies the above-described range, satisfactory hole transporting characteristics can be obtained without substantially lowering the driving voltage.

A light emitting layer (EML) can 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 an aromatic heterocyclic compound of the general formula (1) as described above. At this time, an aromatic heterocyclic compound of the formula (1) can be used as a dopant and can be used together with a suitable known host material, and furthermore, a known dopant material can be included. In addition to the known dopant materials, the aromatic heterocyclic compound of Formula 1 may be used as a host. On the other hand, it is also possible to use the aromatic heterocyclic compound of Formula 1 alone. For example, Alq3 or CBP (4,4'-N, N'-dicarbazole-biphenyl) or PVK (poly (n- Vinylcarbazole), 9,10-dinaphthylanthracene (ADN), and the like, but the present invention is not limited thereto.

PVK ADN

Meanwhile, PtOEP, Ir (piq) ₃ , Btp ₂ Ir (acac), and DCJTB may be used as known red dopants that can be used in addition to the aromatic heterocyclic compound represented by Formula 1, but the present invention is not limited thereto.

Ir (ppy) ₃ (ppy = phenylpyridine), Ir (ppy) ₂ (acac), Ir (mpyp) ₃ and C545T may be used as the known green dopant. However, the present invention is not limited thereto.

On the other hand, as known blue dopants, F ₂ Irpic, (F ₂ ppy) ₂ Ir (tmd), Ir (dfppz) ₃ , ter-fluorene, 4,4'- (DPAVBi), 2,5,8,11-tetra- t -butylperylene (TBP), and the like can be used, but the present invention is not limited thereto.

               DPAVBI TBP

When the dopant and the host are used together, the doping concentration of the dopant 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 Å to 1000 Å, preferably 200 Å to 600 Å. When the thickness of the light-emitting layer satisfies the above-described range, excellent luminescence characteristics can be exhibited without substantial drop in driving voltage.

When the phosphorescent dopant is used together with the phosphorescent dopant, a method such as vacuum evaporation, spin coating, casting, or LB method is used between the electron transporting layer and the light emitting layer to prevent the triplet excitons or holes from diffusing into the electron transporting layer The hole blocking layer HBL can be formed. In the case of forming the hole blocking layer by the vacuum deposition method and the 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. As the hole blocking material, a well-known hole blocking material can be used. Examples of the hole blocking material include oxadiazole derivatives, triazole derivatives, and phenanthroline derivatives.

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 satisfies the above-described range, excellent hole blocking characteristics can be obtained without substantially lowering the driving voltage.

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 (Cathode), and an aromatic heterocyclic compound represented by the above-mentioned formula (1) can be used. Alternatively, known materials such as quinoline derivatives, particularly tris (8-quinolinolate) aluminum (Alq3), TAZ and Balq, which are known electron transporting materials, may be used, but the present invention is not limited thereto.

TAZ

The thickness of the electron transporting layer may be about 100 ANGSTROM to 1000 ANGSTROM, preferably 150 ANGSTROM to 500 ANGSTROM. When the thickness of the electron transporting layer satisfies the above-described range, satisfactory electron transporting characteristics can be obtained without substantially lowering the driving voltage.

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-forming material, an aromatic heterocyclic compound of the above-mentioned formula (1) can be used. Alternatively, any material known as an electron injection layer forming material such as LiF, NaCl, CsF, Li2O, 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. When the thickness of the electron injection layer satisfies the above-described range, satisfactory electron injection characteristics can be obtained without substantially lowering the driving voltage.

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.

According to an embodiment of the present invention, there is provided a method of manufacturing an organic light emitting diode, comprising: forming a first electrode; forming an organic film including an aromatic heterocyclic compound represented by Formula 1 on the first electrode; And forming a second electrode on the organic layer. At this time, the organic layer may be a light emitting layer, a hole injecting layer, a hole transporting layer, a hole blocking layer, or an electron transporting layer. The method of manufacturing the organic light emitting device may further include forming at least one layer selected from the group consisting of a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer, an electron transport layer, and an electron injection layer .

The organic film formation step including the aromatic heterocyclic compound represented by Formula 1 may be carried out by applying a solution such as a vacuum evaporation method or a spin coating method, an inkjet printing method, a screen printing method, a casting method, an LB method, a spray printing method, Method. Further, an organic film containing an aromatic heterocyclic compound represented by the above formula (1) is formed on the donor film by the vacuum deposition method or the solution coating method as described above, and then thermally transferred to the substrate on which the first electrode or the like is formed . &Lt; / RTI &gt;

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.

[Example]

Synthetic example  One

The following compound 1 was synthesized according to the following reaction scheme 1:

(3-bromophenyl) -5H-pyrido [3,2-b] indole) (3 g, 9.28 mmol) was added to a solution of 5- (3-bromophenyl) -5H- 2- (9-phenylanthracen-10-yl) -4,4,5,5-tetramethyl- [l, 3,2] -dioxaborolane 4,4,5,5-tetramethyl- [1,3,2] -dioxaborolane (4.24 g, 11.14 mmol), tetrakis (triphenylphosphine) palladium [0] (0.54 g, 0.464 mmol) was dissolved in THF (60 mL), sodium carbonate aqueous solution (20 mL, 11.14 mmol) was added, and the mixture was refluxed for 24 hours. After refluxing, the reaction mixture was extracted with methylene chloride and purified by column chromatography to obtain 5- (3- (10-phenylanthracen-9-yl) phenyl) -5H-pyrido [3,2-b ] Indole (3.9 g, 84.6%) was obtained in the same manner as in Example 1, except that 5- (3- (10-phenylanthracen-9-yl) phenyl) -5H- pyrido [3,2-

^{1 H NMR (300 MHz, CDCl} 3) δ 7.30-7.89 (m, 22H), 8.47 (d, J = 7.6 Hz, 1H), 8.62 (d, J = 4.7 Hz, 1H)

Thermal analysis using TGA (Thermo Gravimetric Analysis) and DSC (Differential Scanning Calorimetry) for the compound 1 (N ₂ atmosphere, temperature range: room temperature ~ (10 ℃ / min 600 ℃ ) - TGA, -DSC from room temperature to 400 ℃ , Pan Type: Pt Pan in Disposable Al Pan (TGA), Disposable Al pan (DSC)), the compound 1 had a Tg of 117 캜, Tm of 279 캜, and Td of 331 캜. MS chromatogram of Compound 1 is as shown in FIG. 2, DSC data of Compound 1 is as shown in FIGS. 3A and 3B, and TGA data of Compound 1 is as shown in FIG. The UV and PL data of the film are as shown in Fig.

Meanwhile, the HOMO of the compound 1 was -5.249 eV, the LUMO was -1.767 eV, and the energy gap was 3.482 eV (calculated above). On the other hand, the HOMO observed value of Compound 1 was -5.89 eV, the LUMO was -2.90 eV, and the energy gap was 2.99 eV (the above is the actual value from AC2 and UV edge)

Synthetic example  2

The following compound 6 was synthesized according to the following reaction scheme 2:

5H-pyrido [3,2-b] indole (1.6 g, 4.93 mmol) was added to a solution of 5- (3-bromophenyl) -5H- , 4,4,5,5-tetramethyl-2- (10- (3- (naphthalen-2-yl) phenyl) anthracene-9-yl) -1,3,2-dioxaborolane , 5,5-tetramethyl-2- (10- (3- (naphthalen-2-yl) phenyl) anthracen-9-yl) -1,3,2- dioxaborolane (3 g, 5.92 mmol) (0.29 g, mmol) was dissolved in THF (50 mL), and an aqueous sodium carbonate solution (15 mL, 5.92 mmol) was added to the solution And refluxed for 24 hours. After refluxing, the mixture was extracted with methylene chloride (methylene chloride) and purified by column chromatography (column chromatography) to obtain 5- (3- (10- (3- (naphthalen- ) Anthracen-9-yl) phenyl) -5H-pyrido [3,2- b] indole (5- (3- (10- ) -5H-pyrido [3,2-b] indole) was obtained in an amount of 2.7 g (88%).

^{1 H NMR (300 MHz, CDCl} 3) δ 7.38-7.96 (m, 28H), 8.14 (d, J = 9.4 Hz, 1H), 8.63 (d, J = 4.8 Hz, 1H)

Thermal analysis using TGA (Thermo Gravimetric Analysis) and DSC (Differential Scanning Calorimetry) for the compound 6 (N ₂ atmosphere, temperature range: room temperature ~ (10 ℃ / min 600 ℃ ) - TGA, -DSC from room temperature to 400 ℃ , Pan Type: Pt Pan in Disposable Al Pan (TGA), Disposable Al pan (DSC)), Tg of the compound 6 was 137 占 폚, Tm was 286 占 폚, and Td was 483 占 폚. MS chromatogram of Compound 6 is as shown in Fig. 6, DSC data of Compound 6 is as shown in Figs. 7a and 7b, and TGA data of Compound 6 is as shown in Fig.

On the other hand, the LUMO of the compound 6 was -1.774 eV, the HOMO was -5.250 eV, and the energy gap was 3.475 (calculated value).

Synthetic example  3

The following compound 7 was synthesized according to the following reaction scheme 3:

(3-bromophenyl) -5H-pyrido [3,2-b] indole) (4.73 g, 14.63 mmol) , 4,4,5,5-tetramethyl-2- (10- (3- (naphthalen-2-yl) anthracene-9-yl) -1,3,2-dioxaborolane (7.56 g, 17.56 mmol), tetrakis (triphenylphosphine) palladium (0.84 g, 0.73 mmol) was dissolved in THF (90 mL), an aqueous solution of sodium carbonate (30 mL, 17.56 mmol) was added, and 24 Lt; / RTI &gt; After refluxing, the mixture was extracted with methylene chloride (methylene chloride) and purified by column chromatography (column chromatography) to obtain 5- (3 (10 (naphthalene- Yl) phenyl) -5H-pyrido [3,2-b] indole (prepared from 5- (3- (10- (naphthalen-2-yl) anthracen- ) Was obtained in an amount of 5.6 g (70.0%).

¹ H NMR (300 MHz, CDCl ₃ )? 7.26-7.47 (m, 6H), 7.58-8.11 (m, 19H), 8.6 (d, J =

Thermal analysis using TGA (Thermo Gravimetric Analysis) and DSC (Differential Scanning Calorimetry) of the above compound 7 (N ₂ atmosphere, temperature range: room temperature ~ (10 ℃ / min 600 ℃ ) - TGA, -DSC from room temperature to 400 ℃ , Tg of the compound 7 was 139 占 폚, Tm was 344 占 폚, and Td was 447 占 폚, by means of a disposable Al pan (TGA) and a disposable Al pan (DSC). MS chromatogram of compound 7 is as shown in Fig. 9, DSC data of compound 7 is as shown in Figs. 10a and 10b, and TGA data of compound 7 is as shown in Fig.

On the other hand, the LUMO of the compound 7 was -1.764 eV, the HOMO was -5.274 eV, and the energy gap was 3.511 eV (calculated value).

Evaluation example   1: Evaluation of luminescence property of compound (solution state)

The luminescent characteristics were evaluated by evaluating the UV absorption spectrum and the PL (photoluminescence) spectrum of Compound 1 above. Compound 1 was diluted in toluene to a concentration of 0.2 mM and the UV absorption spectrum was measured using a Shimadzu UV-350 Spectrometer. Meanwhile, Compound 1 was diluted in toluene to a concentration of 10 mM, and a PL (Photoluminecscence) spectrum was measured using an ISC PC1 Spectrofluorometer equipped with a Xenon lamp. As a result, it was confirmed that the maximum absorption wavelength of the compound 1 was 400 nm, and the maximum wavelength of the PL spectrum was 445 nm.

Example  One

Using Compound 1 as a light emitting layer material, an organic light emitting device having the following structure was manufactured: ITO // HIL (60 nm) // HTL (30 nm) // EML (35 nm) // ETL (0.6 nm) / Al (150 nm).

The anode was prepared by cutting a 15 Ω / cm ² (1000 Å) ITO glass substrate into 50 mm × 50 mm × 0.7 mm size, ultrasonically cleaning the substrate in acetone isopropyl alcohol and pure water for 15 minutes, and then rinsing the substrate with UV ozone for 30 minutes. M-MTDATA as a hole injection layer material was vacuum deposited on the ITO anode at a deposition rate of 1 ANGSTROM / sec to form a hole injection layer having a thickness of 60 nm, followed by vacuum deposition of? -NPD at a deposition rate of 1 ANGSTROM / A hole transport layer was formed on the hole transport layer, and Compound 1 was vacuum deposited on the hole transport layer at a rate of 1 Å / sec to form a 35 nm thick emission layer. Then, Alq3 was vacuum-deposited on the light emitting layer to form an electron transporting layer having a thickness of 25 nm, and then LiF 0.6 nm (electron injecting layer) and Al 150 nm (cathode) were sequentially vacuum-deposited on the electron transporting layer, An organic light emitting device as shown in FIG. This is referred to as sample 1.

Example  2

Example 1 was repeated except that Compound 1 was used as a host in the light emitting layer and DPAVBi was also used as a dopant (doping concentration 5 wt%) in Example 1 instead of Compound 1 alone as the light emitting layer material. An organic light emitting device was fabricated using the same method as that of the organic light emitting device. This is referred to as sample 2. Compound 1 (host) and DPAVBi (dopant) were deposited at deposition rates of 1 Å / sec and 0.05 Å / sec, respectively.

Example  3

An organic light emitting device was fabricated in the same manner as in Example 2, except that the thickness of the HTL was 20 nm. This is referred to as sample 3.

Example  4

In Example 2, instead of using Compound 1 as a host in the light emitting layer and DPAVBi as a dopant (doping concentration 5 wt%) and Alq3 as an electron transporting layer material, ADN (9,10-dinaphthyl Except that DPAVBi was used as a dopant (doping concentration: 5 wt%) and Compound 1 was used as an electron transporting layer material, using the same method as the manufacturing method of the organic light emitting device of Example 2 Thereby preparing an organic light emitting device. This is referred to as sample 4.

Comparative Example  One

In Example 2, instead of using Compound 1 as a host in the light emitting layer and DPAVBi as a dopant (doping concentration 5 wt%), ADN (9,10-dinaphthylanthracene) was used as a host in the light emitting layer, dopant The organic light emitting device was fabricated using the same method as the manufacturing method of the organic light emitting device of Example 2 except that DPAVBi was used as the dopant concentration (5 wt%). This is referred to as sample A.

Evaluation example  2

For each of Samples 1 to 4 and A, the driving voltage, power, luminance and chromaticity coordinates were evaluated using a PR650 (Spectroscan) Source Measurement Unit. The results are shown in Table 2 below.

Turn on/Op.V@1000nit Im / W @ 1000nit
(max @ V) Cd / A @ 1000nit
(max @ V) CIE
@ 1000nit Comparative Example 1 3.4V / 6.6V 3.36
(4.73@4.2V) 7.06
(7.15@7.4V) 0.14, 0.26 Example 1 3.4V / 7.8V 0.32
(0.43@4.4V) 0.80
(0.80@7.6V) 0.17, 0.29 Example 2 3.0V / 6.6V 1.11
(1.52@3.6V) 2.34
(2.40@7.4V) 0.15, 0.26 Example 3 2.8V / 6.0V 1.21
(2.14@3.0V) 2.32
(2.37@6.8V) 0.15, 0.28 Example 4 3.4V / 5.6V 2.99
(3.22@4.0V) 5.33
(5.55@6.2V) 0.14, 0.26

On the other hand, evaluation related graphs (L-I-V, current and power efficiency) of Samples 1, 2, 3, 4 and A (Examples 1 to 4 and Comparative Example 1) are shown in FIGS. 12, 13, 14 and 15.

1A to 1C are sectional views schematically showing a structure of an embodiment of an organic light emitting device according to the present invention,

Figure 2 shows the MS chromatographic results of Compound 1,

3A and 3B are DSC data of Compound 1,

4 is a TGA data of Compound 1,

Figure 5 shows the MS chromatographic results of Compound 6,

6 is a diagram showing a UV absorption spectrum and a PL (photoluminescence) spectrum of a solution of Compound 1,

Figures 7a and 7b are DSC data of compound 6,

8 is a TGA data of Compound 6,

9 is the MS chromatographic result of Compound 1,

10A and 10B are DSC data of the compound 1,

11 is a TGA data of Compound 1,

12 to 15 show evaluation related graphs (L-I-V, current and power efficiency) of Samples 1, 2, 3, 4 and A (Examples 1 to 4 and Comparative Example 1).

Claims (15)

An aromatic heterocyclic compound represented by the following formula (1): &Lt; Formula 1 >

In Formula 1, R ₁ to R ₉ are independently of each other hydrogen or any one of the following formulas (3a) to (3i):

R ₁₀ to R ₁₂ are independently of each other hydrogen or any one of the following formulas (2a) to (2o):

a, b and c are 0, 1 or 2; X is CH or N; The method according to claim 1, A compound represented by the formula (1a): <Formula 1a>

delete delete delete delete delete delete The method according to claim 1, 1. A compound represented by the formula: &Lt; EMI ID =

In the above formula (1b) R ₁₀ to R ₁₂ are independently of each other hydrogen or any one of the following formulas (2a) to (2o):

X is CH or N; Q ₃ is hydrogen or an unsubstituted C ₅ -C ₂₀ aryl group. The method according to claim 1, Lt; RTI ID = 0.0 &gt; 1 &lt; / RTI &gt; to 17: &Lt; Compound 1 > < Compound 2 >

&Lt; Compound 3 > < Compound 4 >

&Lt; Compound 5 > < Compound 6 >

&Lt; Compound 7 > < Compound 8 >

&Lt; Compound 9 > < Compound 10 &

&Lt; Compound 11 > < Compound 12 >

&Lt; Compound 13 > < Compound 14 >

&Lt; Compound 15 > < Compound 16 >

<Compound 17>

An organic light emitting device comprising a first electrode, a second electrode, and an organic film containing a compound of any one of claims 1, 2, 9, and 10 between the first electrode and the second electrode. 12. The method of claim 11, Wherein the organic film is a light emitting layer or an electron transporting layer. 12. The method of claim 11, Wherein at least one layer selected from the group consisting of a hole injecting layer, a hole transporting layer, a light emitting layer, a hole blocking layer, an electron transporting layer, and an electron injecting layer is further provided between the first electrode and the second electrode. Forming a first electrode over the substrate; Forming an organic film comprising an aromatic heterocyclic compound of any one of claims 1, 2, 9, and 10 on the first electrode; And Forming a second electrode on the organic layer; Wherein the organic light emitting device comprises a first electrode and a second electrode. 15. The method of claim 14, Wherein the organic film forming step is performed using a vacuum deposition method, a spin coating method, an inkjet printing method, a screen printing method, a spray printing method, or a thermal transfer method.

Images