KR101375361B1 - Organic light compound and organic light device using the same - Google Patents

Abstract

The present invention relates to an organic optical device and an organic optical compound used therein, and more particularly, to an organic light emitting device capable of realizing excellent luminous efficiency, emission brightness, color purity, and emission lifetime, and an organic light emitting compound or solar power generation used therefor. The present invention relates to an optical device for use and an optical compound used therefor, in particular to the development of pyridoimidazole derivatives and organic optical devices using the same, including electron transport layer (ETM), light emitting layer (EML), and hole transport layer (HTM). Various materials such as various organic films between the first electrode and the second electrode may be developed, and performance may be maximized, such as an increase in efficiency and a decrease in driving voltage, and the ability as an OLED material may be maximized.

Description

TECHNICAL FIELD [0001] The present invention relates to an organic light emitting diode (OLED)

The present invention relates to an organic light emitting compound, in particular pyridoimidazole-based derivatives and an organic optical device using the same, and more particularly, to an organic light emitting device capable of realizing excellent luminous efficiency, luminous brightness, color purity and luminous lifetime; The present invention relates to an organic light emitting compound or photovoltaic device for photovoltaic power generation and a photochemical compound used therein.

Generally, an organic light emitting phenomenon refers to a phenomenon in which light appears when electric energy is applied to an organic material. That is, when a voltage is applied between the two electrodes when the organic layer is positioned between the anode and the cathode, holes are injected into the organic layer and holes are injected into the organic layer. When the injected holes and electrons meet, an exciton is formed. When the exciton falls back to the ground state, light is emitted.

The study of organic electroluminescent devices was made by observing luminescence from organic thin films by applying high alternating voltage to polymer thin films containing organic pigments in the 1950s. In 1965, current was applied to an anthracene single crystal to generate singlet excitons, Fluorescence was obtained.

As one method for making an organic electroluminescent device efficiently, research has been conducted to manufacture an organic material layer in a multi-layer structure instead of a single layer. In 1987, an organic electroluminescent device having a multilayer structure divided into a hole layer and a functional layer of a light emitting layer by Tang has been proposed. Most organic electroluminescent devices currently used include a hole injecting hole Layer, a hole-transporting layer for transporting holes, a light-emitting layer for recombining 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 electroluminescent devices are formed in a multi-layer structure is that the moving speeds of holes and electrons are different from each other. Therefore, when an appropriate hole injecting layer, a transfer layer, an electron transporting layer and an electron injecting layer are formed, holes and electrons can be effectively transferred , And a balance between the holes and electrons in the device can be made to improve the luminous efficiency.

The first reports on the materials of electron transport include oxadiazole derivatives (PBD). It has been reported that the triazole derivative (TAZ) and the phenanthroline derivative (BCP) exhibit electron transportability. Organic metal complexes, which have relatively high stability and electron transfer rate, are good candidates for the electron transport layer. Alq3, which is superior in stability and electron affinity, is the most excellent candidate. . In addition,

Known electron transporting materials include flavon derivatives disclosed in Sanyo, or germanium and silicon cyclopentadiene derivatives of Chisso. (Japanese Unexamined Patent Publication No. 1998-017860, Japanese Unexamined Patent Publication No. 1999-087067).

In addition, a number of organic monomolecular materials having imidazole group, oxazole group, and thiazole group have been reported as materials for conventional electron injection and transport layers. However, before these materials were reported as electron transport materials, Motorola's EU0700917 A2 has already reported application of metal complex compounds of these materials to the blue light emitting layer or the cyan light emitting layer of an organic light emitting device.

TPBI disclosed in Kodak Company in 1996 and disclosed in U.S. Patent No. 5,645,948 is known as a typical electron transport layer material having an imidazole group and its structure is composed of three N-phenylbenzene It has an ability to block an electron passing through the light emitting layer as well as an ability to transfer electrons functionally containing an imidazole group, but has a low thermal stability to be applied to an actual device.

In addition, although the electron transporting materials disclosed in JP-A-11-345686 contain an oxazole group and a thiazole group and can also be applied to a light emitting layer, they have come to practical use in terms of driving voltage, luminance, I can not.

Therefore, in order to overcome the problems of the prior art as described above and to further improve the characteristics of the organic EL device, development of a more stable and efficient material that can be used as an electron transporting material in the organic EL device is still required.

A first object of the present invention is to provide a novel organic photo-compound which can be applied to an organic photonic device, particularly an organic electroluminescent device.

A second object of the present invention is to provide an organic electroluminescent device including the novel compound and having a low driving voltage and improved luminous efficiency, brightness, color purity, thermal stability and lifetime, and an organic photonic device for solar power generation .

The organic optical compound according to the present invention and the organic optical device using the same are based on the organic optical compound of formula F:

<Formula F>

In the formula, X is C or N,

R1, R2, R3 and R4 are each independently

A C5-C40 aryl group, a C5-C40 heteroaryl group, a C5-C40 aryloxy group, a C1-C40 alkyloxy group, a C5-C40 arylamino group, A diarylamino group of C40, an arylalkyl group of C6 to C40, a cycloalkyl group of C3 to C40, and a heterocycloalkyl group of C3 to C40; Or a group forming an adjacent group and a fused aliphatic ring, a condensed aromatic ring, a condensed heteroaliphatic ring or a condensed heteroaromatic ring,

One or both of R3 and R4 is always an aryl group of C5 ~ C40 or a heteroaryl group of C5 ~ C40.

The organic optical device according to the present invention provides high luminous efficiency, high luminance, high color purity and remarkably improved luminous lifetime,

In addition, the present invention provides organic light emitting devices and organic light emitting compounds, or organic photoconductors and optical compounds for solar power generation.

Hereinafter, the present invention will be described in detail.

While the present invention has been described in connection with certain embodiments, it is obvious that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the invention. 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. Singular expressions include plural expressions unless the context clearly indicates otherwise. In the present application, the term &quot; comprising &quot; or &quot; consisting of &quot;, or the like, refers to the presence of a feature, a number, a step, an operation, an element, a component, But do not preclude the presence or addition of one or more other features, integers, 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 has been developed an organic light emitting compound, in particular pyridoimidazole-based derivatives, such as electron transport layer (ETM), light emitting layer (EML), hole transport layer (HTM), such as various organic between the first electrode and the second electrode We will present materials that can be used in various ways, such as films, and improve materials such as increased efficiency and reduced driving voltage, and develop materials that maximize their ability as OLED materials.

In the present specification, the term "organic photocompound" means a compound used in an organic photonic device. The scope of the present invention is not limited to the organic luminescent layer. The scope of the present invention is not limited to the organic luminescent layer. Can be used for any layer constituting the substrate.

In this specification, the terms 'optical compound' and 'optical 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 conventional definition It is a selected term.

An organic photonic 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 photo-compound represented by the following formula (F).

<Formula F>

X in the derivative is C or N,

R1, R2, R3 and R4 are each independently

H, D, C1-C40 alkyl group, C5-C40 aryl group, C5-C40 heteroaryl group, C5-C40 aryloxy group, C1-C40 alkyloxy group, C5-C40 arylamino group, C5- ~ C40 diarylamino group, C6 ~ C40 arylalkyl group, C3 ~ C40 cycloalkyl group and C3 ~ C40 heterocycloalkyl group; Or a group which forms a fused aliphatic ring, a fused aromatic ring, a fused heteroaliphatic ring or a fused heteroaromatic ring with an adjacent group,

One or both of R3 and R4 is always an aryl group of C5 ~ C40 or a heteroaryl group of C5 ~ C40.

The inventor of the present invention selects A1, A2, B1 and B2 and X in the substituent of the organic photochemical compound of Formula F,

Developed various derivatives, such as an electron transport layer (ETM), light emitting layer (EML), hole transport layer (HTM), such as organic photo compounds that can be used as various organic films between the first electrode and the second electrode and

We have developed an organic photonic device using it,

It has been found that when the organic electroluminescent device is used as an organic light emitting device, it is possible to improve the performance such as the efficiency increase and the driving voltage decrease, maximize the ability as the OLED material,

It is expected that excellent application efficiency will be obtained when applied to optical devices and optical compound fields for solar power generation.

Hereinafter, the organic photochemical compound of formula (F) will be described in relation to an organic light emitting device, but the present invention should not be construed as limiting.

The organic photochemical compound of Formula F is suitable as a material forming an organic film interposed between the first electrode and the second electrode of the organic optical device. The organic photocompound of Formula F is suitable for use in an organic layer of an organic light emitting device, particularly, a hole transport layer, a hole injection layer, or a light emitting layer, and is used not only as a host material but also as a dopant material. The organic photo compound of Formula F provides a color that is blue to green and is suitable for use in a white light emitting device.

C1 to C40 alkyl group, C2 to C40 alkenyl group, C2 to C40 alkynyl group, C5 to C40 aryl group, C5 to C40 heteroaryl group, C5 to C40 aryl, R1, R2, R3 and R4 Oxy group, C1-C40 alkyloxy group, C5-C40 arylamino group, C5-C40 diarylamino group, C6-C40 arylalkyl group, C3-C40 cycloalkyl group, and C3-C40 heterocycloalkyl group

A substituted or unsubstituted C1 to C40 alkyl group, a substituted or unsubstituted C1 to C40 alkoxy group, a substituted or unsubstituted C1 to C40 amino group, a substituted or unsubstituted C3 to C40 cycloalkyl group, A C 6 to C 40 heteroaryl group, a C 6 to C 40 heteroaryl group, a C 5 to C 40 heteroaryl group, and the like.

Moreover, the said C1-C40 alkyl group of said A1, A2, B1, and B2, the alkenyl group of C2-C40, the alkynyl group of C2-C40, the aryl group of C5-C40, the heteroaryl group of C5-C40, of C5-C40 Introduction to aryloxy group, C1-C40 alkyloxy group, C5-C40 arylamino group, C5-C40 diarylamino group, C6-C40 arylalkyl group, C3-C40 cycloalkyl group and C3-C40 heterocycloalkyl group Out of the substituents

A substituted or unsubstituted C1 to C40 alkyl group, a substituted or unsubstituted C2 to C40 alkenyl group, a substituted or unsubstituted C1 to C40 alkoxy group, a substituted or unsubstituted C1 to C40 amino group, a C3 to C40 cycloalkyl group, a C3 to C40 heterocycloalkyl group, The heteroaryl group of C &lt;

A substituted or unsubstituted C1 to C40 alkyl group, a substituted or unsubstituted C1 to C40 alkoxy group, a substituted or unsubstituted C1 to C40 amino group, a substituted or unsubstituted C3 to C40 cycloalkyl group, At least one second substituent selected from the group consisting of a heterocycloalkyl group of C40, an aryl group of C6 to C40, and a heteroaryl group of C5 to C40; Or to form adjacent condensed aliphatic rings, condensed aromatic rings, condensed heteroaliphatic rings or condensed heteroaromatic rings or spiro bonds.

Furthermore, the alkyl groups of C1 to C40, the alkenyl groups of C2 to C40, the alkynyl groups of C2 to C40, the aryl groups of C5 to C40, the heteroaryl groups of C5 to C40, and the groups of C5 to C40 of A1, A2, B1 and B2 Aryloxy group, C1-C40 alkyloxy group, C5-C40 arylamino group, C5-C40 diarylamino group, C6-C40 arylalkyl group, C3-C40 cycloalkyl group and C3-C40 heterocycloalkyl group Being a substituent

A phenanthryl group, a phenanthryl group, an anthracenyl group, a benzoanthracenyl group, an azranyl group, an acenaphthylenyl group, a phenanthryl group, a phenanthryl group, a phenanthryl group, A phenanthryl group, a phenanthrenyl group, a phenanthrenyl group, a phenanthrenyl group, a pyrenyl group, a chrysenyl group, a picenyl group, a perylenyl group, a chloroperylenyl group, a pentaphenyl group, A phenyl group, a hexacenyl group, a rubicenyl group, a coronenyl group, a trinaphthylenyl group, a heptaphenyl group, a heptacenyl group, a fluorenyl group, a pyranthrenyl group, an obenyl group, a carbazolyl group, a dibenzofuranyl group, A thiophenyl group, a thiophenyl group, an indolyl group, a purinyl group, a benzimidazolyl group, a quinolizinyl group, a quinolinyl group, a benzothiophenyl group, a parathiazinyl group, a pyrrolyl group, a pyrazolyl group, an imidazolyl group, , Thiazolyl group, triazolyl group, tetrazolyl group, oxadiazolyl group, A pyridinyl group, a pyridazinyl group, a pyrimidinyl group, a pyrazinyl group, a thianthrenyl group, a cyclopentyl group, a cyclohexyl group, an oxiranyl group, a pyrrolidinyl group, a pyrazolidinyl group, (C6-C50 aryl) amino group, silyl group, and derivatives thereof are preferable.

The aryl group is a monovalent group having an aromatic ring system and may include two or more ring systems, and the two or more ring systems may exist in a bonded or condensed form to each other. The heteroaryl group refers to a group in which at least one carbon of the aryl group is substituted with at least one member selected from the group consisting of N, O, S, P, Si and Se.

On the other hand, the cycloalkyl group refers to an alkyl group having a ring system, and the heterocycloalkyl group refers to a group in which at least one carbon in the cycloalkyl group is substituted with at least one member selected from the group consisting of N, O, S, P, Si and Se .

When at least one hydrogen of the aryl group and the heteroaryl group is substituted, the substituent is a C1-C50 alkyl group; A C1-C50 alkoxy group; A C6-C50 aryl group unsubstituted or substituted with a C1-C50 alkyl group or a C1-C50 alkoxy group; A C2-C50 heteroaryl group unsubstituted or substituted with a C1-C50 alkyl group or a C1-C50 alkoxy group; A C5-C50 cycloalkyl group which is unsubstituted or substituted by a C1-C50 alkyl group or a C1-C50 alkoxy group and a C5-C50 heterocycloalkyl group which is unsubstituted or substituted by a C1-C20 alkyl group or a C1-C20 alkoxy group, &Lt; / RTI &gt;

In more detail, according to an embodiment of the present invention, the organic photochemical compound used in the organic photoelectric device of the present invention may have a structure of the following formula 1 to 200 (in the present specification, 'formula' is omitted, only numbers). But not limited to:

One

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The organic photochemical compound according to the present invention represented by the compound of Formula F may be synthesized using a conventional synthetic method, and for a more detailed synthetic route of the compound, refer to the schemes of the following Synthesis Examples. The compound of Formula F is suitable for use in an organic film of an organic optical device, particularly a hole transporting layer, a hole injecting 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, an embodiment of an organic light emitting device according to the present invention

First, 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 / a second electrode,

The organic light emitting device may have a structure including a first electrode / a hole injection layer / a hole transport layer / a light emitting layer / an electron transport layer / an electron injection layer / a second electrode,

Further, the organic light emitting device may have 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, one or more of the hole transporting layer, the hole injecting layer, and the light emitting layer may include a compound according to the present invention.

The light-emitting layer of the organic optical 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 optical device according to the present invention will be described with reference to an organic optical device. First, a first electrode material having a high work function on the substrate is formed by a deposition method or a sputtering method to form a first electrode. The first electrode may be an anode. Here, the substrate used in a typical organic optical device is preferably a glass substrate or a transparent plastic substrate having excellent mechanical strength, thermal stability, transparency, surface smoothness, ease of handling, and waterproofness. 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 degree of vacuum of 10 &lt; ^-5 &gt; to 10 &lt; ^-3 &gt; torr, a deposition rate of 0.01 to 100 A / sec and a film thickness of 100 to 1 mu m.

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.

The hole injection layer material may be a compound having the formula a 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) MTDAPB, 2-TNATA (4,4 ', 4 "-tris (N- (2-naphthyl) -N-phenylamino) triphenylamine: 4,4,4- (Polyaniline / dodecylbenzenesulfonic acid) or PEDOT / PSS (poly (3,4-ethylenedioxythiophene) / poly (4-styrenesulfonate)), which is a soluble conductive polymer, Styrene sulfonate), PANI / CSA (polyaniline / camphor sulfonic acid) or PANI / PSS (polyaniline / camphor sulfonic acid)

(Polyaniline) / poly (4-styrenesulfonate): polyaniline) / poly (4-styrenesulfonate)) and the like can be used.

The thickness of the hole injection layer may be about 100 Å to 10000 Å, preferably 100 Å to 1000 Å. If the thickness of the hole injection layer is less than 100 angstroms, the hole injection characteristics may be degraded. If the thickness of the hole injection layer exceeds 10000 angstroms, 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, DNTPD (N, N-bis- [4- (di-m-tolylamino) phenyl] -N, N-diphenylbiphenyl-4,4-diamine) may 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 comprise a compound of formula (a) as described above. Or carbazole derivatives such as N-phenylcarbazole, polyvinylcarbazole and the like, N, N'-bis (3-methylphenyl) -N, N'- diphenyl- [ Amine having an aromatic condensed ring such as N, N'-tetramethyldisiloxane, -4,4'-diamine (TPD) and N, N'-di (naphthalen- The hole transporting layer may have a thickness of about 50 Å to 1000 Å, preferably 100 Å to 600 Å. When the thickness of the hole transporting layer is less than 50 Å, the hole transporting property may be degraded. When the thickness of the hole transporting layer is more than 1000 Å, 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 luminescent layer may comprise a compound of formula (a) according to the invention as described above. At this time, the compound of the formula (a) 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 of formula (a) alone. In the case of the host material, for example, Alq3 (tris (8-hydroxy-quinolatealuminium) or CBP (4,4'-N, N'-dicarbazole- ) Can be used.

In the case of the dopant material, IDE102, IDE105 and IDE55 available from Idemitsu Co., Ltd. and C545T available from Hayashibara Co., Ltd. can be used. As the phosphorescent dopant, red phosphorescent dopant PtOEP, UDC RD61, green phosphorescent dopant Ir (PPy) 3 (PPy = 2-phenylpyridine), a blue phosphorescent dopant F2Irpic, and a red phosphorescent dopant RD 61 manufactured by UDC. MQD (N-methylquinacridone), coumarine derivatives and the like can also be used.

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 Å to 1000 Å, preferably 200 Å to 600 Å.

When the thickness of the light emitting layer is less than 100 Å, the light emitting characteristics may be degraded. If the thickness of the light emitting layer is more than 1000 Å, 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. 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. Known hole blocking materials which can be used, for example, oxadiazole derivatives, triazole derivatives, 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. If the thickness of the hole blocking layer is less than 50 angstroms, the hole blocking characteristics may be deteriorated. If the thickness of the hole blocking layer exceeds 1000 angstroms, the driving voltage may be increased. An organic light emitting element having the structure shown in FIG. 1B is obtained.

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 is a quinoline derivative, particularly a known material such as tris (8-quinolinolate) aluminum (Alq3), TAZ, Balq, Materials may also 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 angstroms, the electron transporting characteristics may be deteriorated. When the thickness of the electron transporting layer exceeds 1000 angstroms, 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, 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. If the thickness of the electron injection layer is less than 1 angstrom, the electron injection characteristics may be deteriorated. If the thickness of the electron injection layer exceeds 100 angstroms, 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 may be represented by Chemical Formula a, and more specifically, may be represented by Chemical Formulas 1 to 161. The details of the compounds are the same as those described for the organic foot and the device described above.

Hereinafter, the reaction examples and comparative 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 reaction examples, the intermediate compounds are indicated by adding the serial number to the final product number. For example, Compound 1 is represented by the compound [1], and the intermediate compound of the above compound is represented by [1-1] or the like. In the present specification, the chemical number is represented by the chemical number. For example, the compound represented by the formula (1) is represented by the compound (1).

[Reaction Example 1] Synthesis of Compound [1]

Preparation of intermediate compound [1-1]

30 g (154.4 mmol) of 2-phenylimidazo [1,2-a] pyridine was dissolved in 1.2 L of tetrahydrofuran under a nitrogen stream in a 2 L reaction flask, and 67.9 mL (169.9 mmol) of butyllithium was added dropwise at -78 ° C. . After stirring for 10 minutes at the same temperature, 45.8 mL (169.9 mmol) of tributyltin chloride were added. After completion of the reaction, the organic layer obtained by layer separation with ethyl acetate / distilled water is removed with anhydrous magnesium sulfate and distilled under reduced pressure. The concentrate was separated and purified through column chromatography to obtain 32.1 g (43%) of an intermediate compound [1-1] as a pale yellow oil.

Preparation of compound [1]

10.3 g (21.38 mmol) of the intermediate compound [1-1], 5 g (19.44 mmol) of 9-bromophenanthrene, and 1.1 g (0.97 mmol) of tetrakis (triphenylphosphine) palladium were added to a 500 mL reaction flask. Under reflux for 12 hours using 250 mL of dimethylformamide. After completion of the reaction, slowly cool to room temperature, and then filter the reaction solution. The filtered solid was washed with methanol and recrystallized with tetrahydrofuran and methanol to give 5.1 g (72%) of the title compound [1] as a yellow solid.

¹ H NMR (300 MHz, CDCl ₃ ): δ 8.83 (m, 2H), 8.38 (m, 1H), 8.02 (m, 2H), 7.83 ~ 7.72 (m, 5H), 7.44 ~ 7.37 (m, 6H) , 7.11 (m, 1 H), 6.76 (m, 1 H)

MS / FAB: 370 (M ⁺ )

Compounds 1 to 14 were prepared according to the method of Reaction Example 1, and the results are shown in the following [Table 1].

[Table 1]

[Reaction Example 2] Synthesis of Compound [15]

Preparation of Intermediate Compound [15-1]

Column chromatograph after reaction at 80 ° C. using an intermediate compound [1-1], 1-bromo-4-iodobenzene, and tetrakis (triphenylphosphine) palladium dimethylformamide in the same manner as in Synthesis Example 1. Separation and purification to synthesize 8g (51%) of the intermediate compound [15-1] as a yellow solid.

Preparation of Intermediate Compound [15-2]

10 g (28.63 mmol) of [15-1] was dissolved in 200 mL of tetrahydrofuran under a nitrogen stream in a 2 L reaction flask, and 12.6 mL (31.49 mmol) of butyllithium were added dropwise at -78 ° C. After stirring for 30 minutes at the same temperature, 4 mL (169.9 mmol) of trimethylborate was added. After completion of the reaction, the reaction mixture was poured into 1N aqueous hydrochloric acid solution and extracted with ethyl acetate. After separation of the organic layer, recrystallization with dichloromethane and normal hexane gave 6.2 g (63%) of an intermediate compound [15-2] as a white solid.

Preparation of Compound [15]

5.8 g (18.66 mmol) of the intermediate compound [15-2], 4 g (15.55 mmol) of 9-bromophenanthrene, 359 mg (0.31 mmol) of tetrakis (triphenylphosphine) palladium, potassium carbonate (K ₂ ) in a 250 mL reaction flask. CO ₃ ) 3.2 g (23.32 mmol) were added thereto, and the mixture was stirred under reflux with 100 mL of 1,4-dioxane and 10 mL of purified water for 12 hours under a nitrogen stream. After completion of the reaction, slowly cool to room temperature, and then filter the reaction solution. The filtered solid was washed with purified water and methanol and recrystallized with dichloromethane and methanol to give 4.8 g (70%) of the title compound [15] as a yellow solid.

¹ H NMR (300 MHz, CDCl ₃ ): δ 8.83 (d, 2H), 8.38 (d, 1H), 8.20 (d, 2H), 8.02 (d, 2H), 7.83 ~ 7.72 (m, 5H), 7.44 ~ 7.37 (m, 6H), 7.15-7.71 (m, 3H), 6.76 (t, 1H)

MS / FAB: 446 (M ⁺ )

Compounds 15 to 36 were prepared according to the method of Reaction Example 2, and the results are shown in the following [Table 2].

[Second group (group)]

[Reaction Example 3] Synthesis of Compound [37]

Preparation of Intermediate Compound [37-1]

In a 500 mL reaction flask, 10 g (57.80 mmol) of 5-bromopyridin-2-amine and 15.9 g (57.80 mmol) of 2-bromo-1,2-diphenylethanone were dissolved in 300 mL of ethanol and refluxed for 12 hours. Cooling to room temperature gave a white solid, which was washed with saturated aqueous NaHCO ₃ and methanol. The residual moisture of the organic layer was removed with anhydrous magnesium sulfate, dried under reduced pressure, and recrystallized with dichloromethane and normal hexane to obtain 15.7 g (78%) of an intermediate compound [37-1] as a yellow solid.

Preparation of Intermediate Compound [37-2]

In the same manner as in Synthesis Example 2, 7 g (60%) of a white solid intermediate compound [37-2] was obtained using an intermediate compound [37-1], butyllithium, trimethylborate, and tetrahydrofuran.

Preparation of Compound [37]

The target compound as a yellow solid using the intermediate compound [37-2], 9-bromophenanthrene, tetrakis (triphenylphosphine) palladium, potassium carbonate, and 1,4-dioxane by the same synthesis method as in Synthesis Example 2. [37] 4.2 g (71%) were obtained.

¹ H NMR (300 MHz, CDCl ₃ ): δ 8.83 (m, 1H), 8.21 (d, 1H), 8.02 (m, 2H), 7.83 ~ 7.69 (m, 7H), 7.50 ~ 7.31 (m, 9H) , 7.15 (m, 1 H), 6.76 (t, 1 H)

MS / FAB: 446 (M ⁺ )

Compounds 37 to 46 were prepared according to the method of Reaction Example 3, and the results are shown in the following [Table 3].

[Table 3]

[Reaction Example 4] Synthesis of Compound [47]

Preparation of intermediate compound [47-1]

Yellow using 3-bromoimidazo [1,2-a] pyridine, phenylboronic acid, tetrakis (triphenylphosphine) palladium, potassium carbonate, 1,4-dioxane in the same synthesis method as in Synthesis Example 2. 14.3 g (78%) of solid intermediate compound [47-1] were obtained.

Preparation of Intermediate Compound [47-2]

20 g (102.97 mmol) of the intermediate compound [47-1] and 18.3 g (102.97 mmol) of N-bromosuccinimide were dissolved in an acetonitrile solvent for 4 hours at room temperature, and then 200 ml of dichloromethane was added thereto. It was washed with% aqueous sodium hydroxide solution and then washed with saturated aqueous sodium thiosulfate solution and water. The residual moisture of the organic layer was removed with anhydrous magnesium sulfate and dried under reduced pressure, and the obtained solid was recrystallized from dichloromethane and methanol to obtain 22.4 g (80%) of an intermediate compound as a yellow solid.

Preparation of Intermediate Compound [47-3]

In the same manner as in Synthesis example 1, 12.3 g (44%) of an intermediate compound [47-3] of a yellow oil was obtained using an intermediate compound [47-2], butyl lithium, and tributyl tin chloride.

Preparation of Compound [47]

4.2 g of the target compound [47] as an intermediate compound [47-3], 9-bromophenanthrene, tetrakis (triphenylphosphine) palladium, and dimethylformamide in the same manner as in Synthesis example 1. %) Was obtained.

¹ H NMR (300 MHz, CDCl ₃ ): δ 8.83 (d, 2H), 8.38 (d, 1H), 8.02 (d, 2H), 7.83 ~ 7.69 (m, 7H), 7.41 ~ 7.31 (m, 3H) , 7.11 (t, 1H), 6.76 (t, 1H)

MS / FAB: 370 (M ⁺ )

Compounds 47 to 71 were prepared according to the method of Reaction Example 4, and the results are shown in the following [Table 4].

[Group 4]

[Reaction Example 5] Synthesis of Compound [72]

Preparation of Intermediate Compound [72-1]

20 g of the intermediate compound [72-1] as a yellow solid using 2-aminenopyridine, 2-bromo-1- (4-bromophenyl) -2-phenylethanone and ethanol in the same manner as in Synthesis example 3 81%) was obtained.

Preparation of Intermediate Compound [72-2]

In the same manner as in Synthesis Example 2, 10.8 g (60%) of an intermediate compound [72-2] was obtained using an intermediate compound [72-1], butyllithium, trimethylborate, and tetrahydrofuran.

Preparation of Compound [72]

The target compound as a yellow solid using the intermediate compound [72-2], 9-bromophenanthrene, tetrakis (triphenylphosphine) palladium, potassium carbonate, and 1,4-dioxane by the same synthesis method as in Synthesis Example 2. [72] 3.8 g (74%) was obtained.

¹ H NMR (300 MHz, CDCl ₃ ): δ 8.83 (d, 2H), 8.38 (d, 1H), 8.20 (d, 2H), 8.02 (d, 2H), 7.83 ~ 7.69 (m, 7H), 7.44 ~ 7.31 (m, 4H), 7.15-7.71 (m, 3H), 6.76 (t, 1H)

MS / FAB: 446 (M ⁺ )

Compounds 72 to 100 were prepared according to the method of Reaction Example 5, and the results are shown in the following [Table 5].

[Fifth group (group)]

[Reaction Example 6] Synthesis of Compound [101]

Preparation of Intermediate Compound [101-1]

6.2 g (40%) of an intermediate compound [101-1] of a yellow oil was obtained using 2-phenylimidazo [1,2-a] pyrimidine, butyllithium, tributyl tin chloride in the same manner as in Synthesis example 1. It was.

Preparation of Compound [101]

3.7 g (68%) of an intermediate compound [101-1], 9-bromophenanthrene, tetrakis (triphenylphosphine) palladium dimethylformamide as a yellow solid in the same manner as in Synthesis Example 1 Was synthesized.

¹ H NMR (300 MHz, CDCl ₃ ): δ 8.95 (d, 2H), 8.85 to 8.80 (m, 2H), 8.14 (d, 2H), 7.95 to 7.84 (m, 5H), 7.53 to 7.49 (m 5H ), 7.30 (t, 1 H)

MS / FAB: 371 (M ⁺ )

101 to 114 compounds were prepared according to the method of Reaction Example 6, and the results are shown in the following [Table 6].

[Table 6]

[Reaction Example 7] Synthesis of Compound [115]

Preparation of Intermediate Compound [115-1]

Column chromatograph after reaction at 80 ° C. using intermediate compound [101-1], 1-bromo-4-iodobenzene, tetrakis (triphenylphosphine) palladium dimethylformamide in the same synthesis method as in reaction example 1 Separation and purification gave 8.3g (52%) of an intermediate compound [115-1] as a yellow solid.

Preparation of Intermediate Compound [115-2]

9.8 g (58%) of a white solid intermediate compound [115-2] was obtained using the intermediate compound [115-1], butyllithium, trimethylborate and tetrahydrofuran in the same manner as in Synthesis example 2.

Preparation of Compound [115]

The target compound as a yellow solid using the intermediate compound [15-2], 9-bromophenanthrene, tetrakis (triphenylphosphine) palladium, potassium carbonate, 1,4-dioxane, in the same manner as in Synthesis Example 2. [115] 3.6 g (72%) were obtained.

¹ H NMR (300 MHz, CDCl ₃ ): δ 8.95 (d, 2H), 8.85 to 8.80 (m, 2H), 8.32 (d, 2H), 8.14 (d, 2H), 7.95 to 7.84 (m, 5H) , 7.53-7.43 (m, 5H), 7.30-7.27 (m, 3H)

MS / FAB: 447 (M ⁺ )

Compounds 115 to 136 were prepared according to the method of Reaction Example 7, and the results are shown in the following [Table 7].

[7th vote group]

[Reaction Example 8] Synthesis of Compound [137]

Preparation of Intermediate Compound [137-1]

Intermediate compound as a yellow solid using 5-bromopyrimidin-2-amine, 2-bromo-1- (4-bromophenyl) -2-phenylethanone, and ethanol in the same manner as in Synthesis example 3. -1] 18.4 g (79%) was obtained.

.

Preparation of Intermediate Compound [137-2]

7.8 g (56%) of an intermediate compound [137-2] was obtained using the intermediate compound [137-1], butyllithium, trimethyl borate, and tetrahydrofuran in the same manner as in Synthesis Example 2.

Preparation of compound [137]

The target compound as a yellow solid using the intermediate compound [137-2], 9-bromophenanthrene, tetrakis (triphenylphosphine) palladium, potassium carbonate, and 1,4-dioxane by the same synthesis method as in Synthesis Example 2. [115] 3.2 g (70%) were obtained.

¹ H NMR (300 MHz, CDCl ₃ ): δ 8.99 ~ 8.92 (m, 4H), 8.12 (d, 2H), 7.92 ~ 7.78 (m, 7H), 7.50 ~ 7.40 (m, 8H)

MS / FAB: 447 (M ⁺ )

Compounds 137 to 146 were prepared according to the method of Reaction Example 8, and the results are shown in the following [Table 8].

[Table 8]

[Reaction Example 9] Synthesis of Compound [147]

Preparation of Intermediate Compound [147-1]

Synthesis method similar to Synthesis Example 2 using 3-bromoimidazo [1,2-a] pyrimidine, phenylboronic acid, tetrakis (triphenylphosphine) palladium, potassium carbonate, 1,4-dioxane 12.3 g (76%) of an intermediate compound [147-1] was obtained as a yellow solid.

Preparation of Intermediate Compound [147-2]

15.7 g (81%) of a yellow solid intermediate compound was obtained using [147-1], N-bromosuccinimide and acetonitrile in the same manner as in Synthesis example 4.

Preparation of Intermediate Compound [147-3]

In the same manner as in Synthesis example 1, 10.3 g (42%) of an intermediate compound [147-3] of a yellow oil was obtained using an intermediate compound [147-2], butyl lithium, and tributyl tin chloride.

Preparation of Compound [147]

3.2 g (72) of the target compound [147] as an intermediate compound [147-3], 9-bromophenanthrene, tetrakis (triphenylphosphine) palladium, and dimethylformamide in the same manner as in Synthesis example 1. %) Was obtained.

¹ H NMR (300 MHz, CDCl ₃ ): δ 8.53 (d, 2H), 8.43-8.38 (m, 2H), 8.02 (d, 2H), 7.83-7.69 (m, 7H), 7.41-7.31 (m, 3H), 7.18 (t, 1H)

MS / FAB: 371 (M ⁺ )

Compounds 147 to 171 were prepared according to the method of Reaction Example 9, and the results are shown in the following [Table 9].

[Table 9 Group]

[Reaction Example 10] Synthesis of Compound [172]

Preparation of Intermediate Compound [172-1]

An intermediate compound of a yellow solid using 2-aminenopyrimidine, 2-bromo-1- (4-bromophenyl) -2-phenylethanone and ethanol in the same manner as in Synthesis example 3 [172-1] 23.4 g (80%) was obtained.

Preparation of Intermediate Compound [172-2]

7.8 g (62%) of an intermediate compound [172-2] as a white solid was obtained using the intermediate compound [172-1], butyl lithium, trimethyl borate, and tetrahydrofuran in the same synthesis method as in Synthesis Example 2.

Preparation of Compound [172]

The target compound as a yellow solid using the intermediate compound [172-2], 9-bromophenanthrene, tetrakis (triphenylphosphine) palladium, potassium carbonate, and 1,4-dioxane by the same synthesis method as in Synthesis Example 2. [172] 3.2 g (71%) were obtained.

¹ H NMR (300 MHz, CDCl ₃ ): δ 8.95 (d, 2H), 8.85-8.80 (m, 2H), 8.32 (d, 2H), 8.14 (d, 2H), 7.91-7.81 (m, 7H) , 7.53-7.43 (m, 3H), 7.31-7.26 (m, 3H)

MS / FAB: 451 (M ⁺ )

172 to 200 compounds were prepared according to the method of Reaction Example 10, and the results are shown in the following [Table 10].

[Table 10]

Comparative Example 1

A compound represented by the following formula (a) is used as a fluorescent green host and a compound (b) represented by the following formula (b) is used as a fluorescent green dopant, and 2-TNATA (4,4 ' 2-yl) -N-phenylamino) -triphenylamine was used as a hole injection layer material and α-NPD (N, N'-di (naphthalene- (30 nm) / Alq3 (30 nm) / LiF (0.5 nm) was used as an organic light emitting device having the following structure: ITO / 2-TNATA (80 nm) /? -NPD ) / Al (60 nm).

An anode was prepared by cutting Corning's 15 Ω / cm ² (1000 Å) ITO glass substrate into 50 mm × 50 mm × 0.7 mm size, ultrasonically cleaning it in acetone isopropyl alcohol and pure water for 15 minutes each, Washed and 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,? -NPD was vacuum deposited to form a hole transport layer having a thickness of 30 nm. Compound (a) represented by Formula (a) and compound (b) represented by Formula (b) (3% doped) were vacuum deposited on the hole transport layer to form a 30 nm thick light emitting layer. Thereafter, a compound c (Alq3) compound represented by Chemical Formula c was vacuum-deposited to a thickness of 30 nm on the emission layer to form an electron transport layer. LiF 0.5 nm (electron injection layer) and Al 60 nm (cathode) were sequentially vacuum deposited on the electron transport layer to prepare an organic light emitting device as shown in Table 12. This is referred to as Comparative Sample 1.

<Formula a><Formulab>

                <Formula c>

Examples 1 to 200

In Comparative Example 1, the same method as in Comparative Example 1 except that Compound 1 to 200 represented by Formulas 1 to 200 disclosed in the Synthesis Example were used as the electron transporting layer compound instead of Compound c (Alq 3) as the electron transporting layer compound. By ITO / 2-TNATA (80nm) / α-NPD (30nm) / Compound a + Compound b (30nm) / Electron Transport Layer Compound 1 ~ 200 / LiF (0.5nm) / Al (60nm) The device was manufactured. These are referred to as samples 1 to 200, respectively.

Evaluation Example 2: Evaluation of Luminescence Characteristics of Comparative Sample 1 and Samples 1 to 200

For Comparative Sample 1 and Samples 1 to 200, luminescence brightness, luminescence efficiency, and luminescence peak were evaluated using Keithley SMU 235 and PR650, respectively, and the results are shown in the following [Table 11]. The samples showed green emission peaks in the range of 516-524 nm.

[Table 11]

As shown in [Table 11] , Samples 1 to 200 exhibited improved luminescence properties compared to Comparative Sample 1.

In the above description, the conventional well-known technique is omitted, but a person skilled in the art can easily guess, deduce and reproduce it.

Claims (10)

delete delete delete delete A first electrode; A second electrode; And an organic optical device comprising at least one organic film between the first electrode and the second electrode, wherein the organic film comprises an organic photo compound represented by the following Chemical Formulas 101 to 200:

delete delete delete delete An organic photochemical compound represented by the following Chemical Formulas 101 to 200: