KR20120083203A - A condensed-cyclic compound and an organic light emitting diode comprising the same - Google Patents

Abstract

PURPOSE: A fused ring compound and an organic light-emitting device including the same are provided to improve heat resistance and light-emitting properties. CONSTITUTION: A fused ring compound is represented by chemical formula 1. The organic light-emitting device comprises a first electrode, a second electrode which faces with the first electrode, and an organic layer placed between the first electrode and the second electrode. The organic layer includes a fused ring compound in the form of combination of single substances or different materials. The organic layer comprises one of a hole injection layer, a hole transport layer, a functional layer which has hole injection function and hole transport function at the same time, an electroluminescence layer, an electron transmission layer and an electron injection layer.

Description

A condensed-cyclic compound and an organic light emitting diode comprising the same

A condensed cyclic compound and an organic light emitting device including the same are provided.

Organic light emitting diodes are self-luminous devices that have a wide viewing angle, excellent contrast, fast response time, excellent luminance, driving voltage and response speed, and are capable of multicoloring.

A general organic light emitting device has an anode formed on the substrate, and may have a structure in which a hole transport layer, a light emitting layer, an electron transport layer and a cathode are sequentially formed on the anode. Here, the hole transport layer, the light emitting layer and the electron transport layer are organic thin films made of an organic compound.

The driving principle of the organic light emitting device having the structure as described above is as follows.

When a voltage is applied between the anode and the cathode, holes injected from the anode move to the light emitting layer via the hole transport layer, and electrons injected from the cathode move to the light emitting layer via the electron transport layer. Carriers such as holes and electrons recombine in the emission layer to generate excitons. The excitons change from excited state to ground state and light is generated.

Provided are a condensed cyclic compound having a novel structure and an organic light emitting device including the same.

There is provided a condensed cyclic compound represented by Formula 1:

≪ Formula 1 >

In Formula 1,

R ₁ is represented by-(Ar ₁ ) _a1- (R ₁₁ ) _b1 , R ₂ is represented _by- (Ar ₂ ) _a2- (R ₁₂ ) _b2 , and R ₃ is represented _by- (Ar ₃ ) _a3- (R ₁₃ ) _b3 , and R _{4 is-} (Ar ₄ ) _a4- (R ₁₄ ) _b4 ;

Ar ₁ to Ar ₄ are each independently a substituted or unsubstituted C ₅ -C ₆₀ aromatic linking group, or a substituted or unsubstituted C ₂ -C ₆₀ Heteroaromatic linking groups;

Ar ₅ and Ar ₆ are each independently a substituted or unsubstituted C ₅ -C ₆₀ arylene group, or a substituted or unsubstituted C ₂ -C ₆₀ heteroarylene group;

R ₅ , R ₆ and R ₁₁ to R ₁₄ are independently of each other hydrogen, deuterium, unshared electron pairs, substituted or unsubstituted C ₁ -C ₆₀ alkyl groups, substituted or unsubstituted C ₂ -C ₆₀ alkenyl groups, substituted or Unsubstituted C ₂ -C ₆₀ alkynyl group, substituted or unsubstituted C ₁ -C ₆₀ alkoxy group, substituted or unsubstituted C ₃ -C ₆₀ cycloalkyl group, substituted or unsubstituted C ₅ -C ₆₀ aryl group, A substituted or unsubstituted C ₅ -C ₆₀ aryloxy group, a substituted or unsubstituted C ₅ -C ₆₀ arylthio group, a substituted or unsubstituted C ₂ -C ₆₀ heteroaryl group, or a substituted or unsubstituted C _2- A C ₆₀ condensed cyclic group;

A1 to a4 are each independently an integer of 0 to 3;

B1 to b4 are each independently an integer of 1 to 5;

c and d are, independently from each other, an integer from 0 to 3;

X ₁ to X ₁₀ are each independently hydrogen, deuterium, halogen atom, hydroxyl group, cyano group, nitro group, amino group, amidino group, hydrazine, hydrazone, carboxyl group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid or Salts thereof, substituted or unsubstituted C ₁ -C ₆₀ alkyl groups, substituted or unsubstituted C ₂ -C ₆₀ alkenyl groups, substituted or unsubstituted C ₂ -C ₆₀ alkynyl groups, substituted or unsubstituted C ₁ -C ₆₀ alkoxy group, substituted or unsubstituted C ₃ -C ₆₀ cycloalkyl group, substituted or unsubstituted C ₅ -C ₆₀ aryl group, substituted or unsubstituted C ₅ -C ₆₀ aryloxy group, substituted or unsubstituted C _{A 5} -C ₆₀ arylthio group, a substituted or unsubstituted C ₂ -C ₆₀ heteroaryl group, -Si (R ₂₁ ) (R ₂₂ ) (R ₂₃ ) or -N (R ₂₄ ) (R ₂₅ );

R ₂₁ to R ₂₅ are each independently hydrogen, deuterium, substituted or unsubstituted C ₁ -C ₆₀ alkyl group, a substituted or unsubstituted C ₂ -C ₆₀ alkenyl group, a substituted or unsubstituted C ₂ -C ₆₀ alkynyl Nyl group, substituted or unsubstituted C ₁ -C ₆₀ alkoxy group, substituted or unsubstituted C ₃ -C ₆₀ cycloalkyl group, substituted or unsubstituted C ₅ -C ₆₀ aryl group, substituted or unsubstituted C ₅ -C ₆₀ aryloxy group, substituted or unsubstituted C ₅ -C ₆₀ arylthio group, or substituted or unsubstituted C ₂ -C ₆₀ heteroaryl group.

In addition, the first electrode; A second electrode opposed to the first electrode; And an organic layer interposed between the first electrode and the second electrode, wherein the organic layer includes the condensed cyclic compound in the form of a single material or a combination of different materials.

Since the condensed cyclic compound represented by Chemical Formula 1 may provide excellent heat resistance and light emission characteristics, the driving voltage, efficiency, brightness, quantum efficiency, lifespan, etc. of the organic light emitting device employing the same may be improved.

1 is a view schematically showing an embodiment of an organic light emitting device.
2 is a graph showing the life characteristics of Examples 1 to 4 and Comparative Example 1.
3 is a graph showing the life characteristics of Examples 5 to 8 and Comparative Example 2.
4 is a graph showing changes in current density and voltage in Examples 1 to 4 and Comparative Example 1. FIG.
5 is a graph showing changes in current density and voltage in Examples 5 to 8 and Comparative Example 2. FIG.

The condensed cyclic compound is represented by the following Chemical Formula 1:

≪ Formula 1 >

In Formula 1, R ₁ is represented by-(Ar ₁ ) _a1- (R ₁₁ ) _b1 , R ₂ is represented _by- (Ar ₂ ) _a2- (R ₁₂ ) _b2 , and R ₃ is-(Ar ₃ ) _a3- (R ₁₃ ) _b3 , and R ₄ is represented _by- (Ar ₄ ) _a4- (R ₁₄ ) _b4 .

R ₁₁ to R ₁₄ are each independently hydrogen, deuterium, a lone pair, a substituted or unsubstituted C ₁ -C ₆₀ alkyl group, a substituted or unsubstituted C ₂ -C ₆₀ alkenyl group, a substituted or unsubstituted C ₂ -C ₆₀ alkynyl group, substituted or unsubstituted C ₁ -C ₆₀ alkoxy group, substituted or unsubstituted C ₃ -C ₆₀ cycloalkyl group, substituted or unsubstituted C ₅ -C ₆₀ aryl group, substituted or unsubstituted C ₅ -C ₆₀ aryloxy group, substituted or unsubstituted C ₅ -C ₆₀ arylthio group, substituted or unsubstituted C ₂ -C ₆₀ heteroaryl group or substituted or unsubstituted C ₂ -C ₆₀ condensed cyclic group Can be.

For example, R ₁₁ to R ₁₄ are each independently hydrogen, deuterium, a substituted or unsubstituted C ₁ -C ₁₀ alkyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted pentalenyl group, Substituted or unsubstituted indenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted azulenyl, substituted or unsubstituted heptalenyl, substituted or unsubstituted Indansenyl, substituted or unsubstituted acenaphthyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted phenalenyl, substituted or unsubstituted phenanthrenyl group (phenanthrenyl), substituted or unsubstituted anthryl group, substituted or unsubstituted fluoranthenyl group, substituted or unsubstituted triphenylenyl group, substituted or unsubstituted pyrenyl group (pyrenyl), substituted or unsubstituted chrysenyl group ( chrysenyl), substituted or unsubstituted naphthacenyl group, substituted or unsubstituted picenyl group, substituted or unsubstituted perylenyl group, substituted or unsubstituted pentaxenyl group (pentaphenyl) , Substituted or unsubstituted hexacenyl group, substituted or unsubstituted cyclopentyl group, substituted or unsubstituted cyclohexyl group, substituted or unsubstituted cycloheptyl group, substituted or unsubstituted dihydronaphthyl group, It may be a substituted or unsubstituted tetrahydronaphthyl group, or a substituted or unsubstituted dihydro-indenyl group, but is not limited thereto.

According to an embodiment, R ₁₁ to R ₁₄ are each independently of the other hydrogen; heavy hydrogen; C ₁ -C ₁₀ alkyl group; Phenyl group; Naphthyl group; Phenanthrenyl group; Fluorenyl group; Pyrenyl group; Cyclopentyl group; Cyclohexyl group; Tetrahydronaphthyl group; Dihydro-indenyl group; And deuterium, halogen atom, hydroxyl group, cyano group, nitro group, amino group, amidino group, hydrazine, hydrazone, carboxyl group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid or salt thereof, C ₁ -C ₆₀ alkyl group, C Phenyl group, naphthyl group, phenanthre substituted with one or more of ₂ -C ₆₀ alkenyl group, C ₂ -C ₆₀ alkynyl group, C ₁ -C ₆₀ alkoxy group, -Si (Q ₁ ) (Q ₂ ) (Q ₃ ) A silyl group, a fluorenyl group, a pyrenyl group, a cyclopentyl group, a cyclohexyl group, a tetrahydronaphthyl group and a dihydro-indenyl group; It may be one of the.

For example, R ₁₁ to R ₁₄ may be represented by any one of hydrogen, deuterium, or the following Chemical Formulas 2A to 2K, but are not limited thereto.

In Formulas 2A to 2K, Z ₁ to Z ₄ are each independently hydrogen, deuterium, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an amino group, an amidino group, a hydrazine, a hydrazone, a carboxyl group, or a salt thereof; Sulfonic acid groups or salts thereof, phosphoric acid or salts thereof, C ₁ -C ₆₀ alkyl groups (e.g., C ₁ -C ₁₀ alkyl groups), C ₂ -C ₆₀ alkenyl groups (e.g., C ₂ -C ₁₀ alkenyl groups), C ₂ -C ₆₀ alkynyl group (eg C ₂ -C ₁₀ alkynyl group), C ₁ -C ₆₀ alkoxy group (eg C ₁ -C ₁₀ alkoxy group) or -Si (Q ₁ ) (Q ₂ ) (Q ₃ ); p is an integer from 1 to 11; q is an integer of 1-4. Herein, Q ₁ to Q ₃ may be each independently a C ₁ -C ₁₀ alkyl group or a C ₅ -C ₁₄ aryl group.

For example, in Formulas 2A to 2K, Z ₁ to Z ₄ independently of each other, hydrogen, deuterium, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an amino group, an amidino group, a hydrazine, a hydrazone, and a carboxyl group Salts thereof, sulfonic acid groups or salts thereof, phosphoric acid or salts thereof, methyl groups, ethyl groups, propyl groups, butyl groups, pentyl groups, methoxy groups, ethoxy groups, propoxy groups, butoxy groups, pentoxy groups, or -Si (Q ₁ ) (Q ₂ ) (Q ₃ ); Q ₁ to Q ₃ may be independently of each other, a C ₁ -C ₁₀ alkyl group (eg, methyl group, ethyl group, propyl group, butyl group, pentyl group, etc.).

In Formulas 2A to 2K, * indicates a binding site to “N” in Formula 1 when each of a1 to a4 is 0, and Ar ₁ to Ar ₄ when each of a1 to a4 is not 0. It represents the binding site with.

In Formula 1, Ar ₁ to Ar ₄ are each independently a substituted or unsubstituted C ₅ -C ₆₀ aromatic linking group, or a substituted or unsubstituted C ₂ -C ₆₀ Heteroaromatic linking group. Ar ₁ to Ar ₄ may be a divalent linking group (for example, see Formula 3A below), a trivalent linking group (for example, see Formula 3C below), depending on the number of R ₁₁ to R ₁₄ bonded thereto; It may be a tetravalent linking group, a pentavalent linking group, or the like, which can be easily understood with reference to compounds 1 to 78 which are specific examples of the condensed cyclic compound.

In Formula 1, Ar ₁ to Ar ₄ independently of each other, a substituted or unsubstituted benzene linkage, a substituted or unsubstituted pentalene linkage, a substituted or unsubstituted indene linkage, a substituted or unsubstituted naphthalene linkage, a substitution or Unsubstituted azulene linkage, substituted or unsubstituted heptalene linkage, substituted or unsubstituted indacene linkage, substituted or unsubstituted acenaphthalene linkage, substituted or unsubstituted fluorene linkage, substituted or unsubstituted phenylene Linking groups, substituted or unsubstituted phenanthrene linking groups, substituted or unsubstituted anthracene linking groups, substituted or unsubstituted fluoranthene linking groups, substituted or unsubstituted triphenylene linking groups, substituted or unsubstituted pyrene linking groups, substituted or Unsubstituted chrysene linkages, substituted or unsubstituted naphthacene linkages, substituted or unsubstituted pysene linkages, substituted or unsubstituted perylenes It may be a linking group, a substituted or unsubstituted pentacene linking group, or a substituted or unsubstituted hexacene linking group.

For example, Ar ₁ to Ar ₄ may be represented by one of the following Chemical Formulas 3A to 3G independently of each other:

In Formulas 3A to 3G, Z ₁₁ to Z ₁₄ are each independently hydrogen, deuterium, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an amino group, an amidino group, a hydrazine, a hydrazone, a carboxyl group, or a salt thereof; Sulfonic acid groups or salts thereof, phosphoric acid or salts thereof, C ₁ -C ₆₀ alkyl groups (e.g., C ₁ -C ₁₀ alkyl groups), C ₂ -C ₆₀ alkenyl groups (e.g., C ₂ -C ₁₀ alkenyl groups), C ₂ -C ₆₀ alkynyl group (eg C ₂ -C ₁₀ alkynyl group), C ₁ -C ₆₀ alkoxy group (eg C ₁ -C ₁₀ alkoxy group); s is an integer from 1 to 6; t may be an integer from 1 to 3.

For example, in Formulas 3A to 3G, Z ₁₁ to Z ₁₄ are each independently hydrogen, deuterium, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an amino group, an amidino group, a hydrazine, a hydrazone, or a carboxyl group. Or salts thereof, sulfonic acid groups or salts thereof, phosphoric acid or salts thereof, methyl groups, ethyl groups, propyl groups, butyl groups, pentyl groups, methoxy groups, ethoxy groups, propoxy groups, butoxy groups, or pentoxy groups, but are not limited thereto. It is not.

* In Formulas 3A to 3G represents a binding site with "N" in Formula 1, and * 'represents a binding site with each of R ₁₁ to R ₁₄ .

In Formula 1, a1 to a4 may be each independently an integer of 0 to 3, and b1 to b4 may be an integer of 1 to 5 independently of each other. For example, a1 to a4 may be 0, 1 or 2 independently of each other, and b1 to b4 may be 1 or 2 independently of each other, but is not limited thereto. When a1 is 2 or more, two or more Ar ₁ may be the same or different from each other. When a2 is 2 or more, two or more Ar ₂ may be the same or different from each other. When a3 is 2 or more, two or more Ar ₃ may be different from each other. It may be the same or different, and when a4 is 2 or more, two or more Ar ₄ may be the same or different from each other. In addition, when b1 is 2 or more, two or more R ₁₁ may be the same as or different from each other, when b2 is 2 or more, two or more R ₁₂ may be the same or different from each other, and when b3 is 2 or more, two or more R ₁₃ may be identical to each other. Or may be different, and when b4 is 2 or more, two or more R ₁₄ may be the same or different from each other.

With reference to the above, in Formula 1, R ₁ to R ₄ may be selected independently from each other. For example, R ₁₁ to R ₁₄ are each independently hydrogen; heavy hydrogen; C ₁ -C ₁₀ alkyl group; Phenyl group; Naphthyl group; Phenanthrenyl group; Fluorenyl group; Pyrenyl group; Cyclopentyl group; Cyclohexyl group; Tetrahydronaphthyl group; Dihydro-indenyl group; And deuterium, halogen atom, hydroxyl group, cyano group, nitro group, amino group, amidino group, hydrazine, hydrazone, carboxyl group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid or salt thereof, C ₁ -C ₆₀ alkyl group, C Phenyl group, naphthyl group, phenanthre substituted with one or more of ₂ -C ₆₀ alkenyl group, C ₂ -C ₆₀ alkynyl group, C ₁ -C ₆₀ alkoxy group, -Si (Q ₁ ) (Q ₂ ) (Q ₃ ) A silyl group, a fluorenyl group, a pyrenyl group, a cyclopentyl group, a cyclohexyl group, a tetrahydronaphthyl group and a dihydro-indenyl group; One of the above, wherein Q ₁ to Q ₃ are each independently a C ₁ -C ₁₀ alkyl group or a C ₅ -C ₁₄ aryl group; Ar ₁ to Ar ₄ may be independently selected from each other, and R ₁ to R ₄ may be independently selected from each other to be represented by any one of Formulas 3A to 3G.

Alternatively, R ₁₁ to R ₁₄ may be independently of each other, hydrogen, deuterium, and any one of Formulas 2A to 2K, and Ar ₁ to Ar ₄ may be independently of each other and represented by any one of Formulas 3A to 3G, ₁ to R ₄ may be selected independently from each other, but are not limited thereto.

R ₁ to R ₄ in Formula 1 may be the same or different from each other.

In Formula 1, Ar ₅ and Ar ₆ may be each independently hydrogen, deuterium, a substituted or unsubstituted C ₅ -C ₆₀ arylene group, or a substituted or unsubstituted C ₂ -C ₆₀ heteroarylene group. .

For example, Ar ₅ and Ar ₆ are each independently a substituted or unsubstituted C ₁ -C ₁₀ alkyl group, a substituted or unsubstituted phenylene group, a substituted or unsubstituted pentalenylene group, a substituted or unsubstituted A nylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted azulenylene group, a substituted or unsubstituted heptalylene group, a substituted or unsubstituted indasenylene group, a substituted or unsubstituted acenaphthylene group, Substituted or unsubstituted fluorenylene group, substituted or unsubstituted phenenylene group, substituted or unsubstituted phenanthrenylene group, substituted or unsubstituted anthylene group, substituted or unsubstituted fluoranthhenylene group, substituted or Unsubstituted triphenylenylene group, substituted or unsubstituted pyrenylene group, substituted or unsubstituted chrysenylene group, substituted or unsubstituted naphthasenylene group, substituted or unsubstituted pisenylene group, substituted or unsubstituted peryl A lenylene group, a substituted or unsubstituted pentaxenylene group, or a substituted or unsubstituted hexasenylene group.

For example, R ₅ and R ₆ are each independently hydrogen; heavy hydrogen; C ₁ -C ₁₀ alkyl group; Phenyl group; Naphthyl group; And deuterium, halogen atom, hydroxyl group, cyano group, nitro group, amino group, amidino group, hydrazine, hydrazone, carboxyl group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid or salt thereof, C ₁ -C ₆₀ alkyl group (eg For example, methyl group, ethyl group, propyl group, butyl group, pentyl group and the like), C ₂ -C ₆₀ alkenyl group, C ₂ -C ₆₀ alkynyl group and C ₁ -C ₆₀ alkoxy group (for example, methoxy group, ethoxy A phenyl group and a naphthyl group substituted with at least one of a period, a propoxy group, a butoxy group, a pentoxy group, and the like; It may be one of, but is not limited thereto.

In Formula 1, c and d may be each independently an integer of 0 to 3. For example, c and d may be 0 or 1 independently of each other, but are not limited thereto.

In Formula 1, R ₅ and R ₆ may be connected to each other with a single bond, a linking group of Formula 4A, or a linking group of Formula 4B:

<Formula 4A> <Formula 4B>

In Formulas 4A and 4B, X ₂₁ to X ₂₃ may be each independently hydrogen, deuterium, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an amino group, an amidino group, a hydrazine, a hydrazone, a carboxyl group, or a salt thereof. Sulfonic acid groups or salts thereof, phosphoric acid or salts thereof, substituted or unsubstituted C ₁ -C ₆₀ alkyl groups, substituted or unsubstituted C ₂ -C ₆₀ alkenyl groups, substituted or unsubstituted C ₂ -C ₆₀ alkynyl groups, substituted or Unsubstituted C ₁ -C ₆₀ alkoxy group, substituted or unsubstituted C ₃ -C ₆₀ cycloalkyl group, substituted or unsubstituted C ₅ -C ₆₀ aryl group, substituted or unsubstituted C ₅ -C ₆₀ aryloxy group , A substituted or unsubstituted C ₅ -C ₆₀ arylthio group, or a substituted or unsubstituted C ₂ -C ₆₀ heteroaryl group.

For example, in Formulas 4A and 4B, X ₂₁ to X ₂₃ may be each independently selected from hydrogen; heavy hydrogen; A halogen atom; Hydroxyl group; Cyano group; A nitro group; An amino group; Amidino groups; Hydrazine; Hydrazone; Carboxyl groups or salts thereof; Sulfonic acid groups or salts thereof; Phosphoric acid or salts thereof; C ₁ -C ₁₀ alkyl group; Phenyl group; Naphthyl group; And deuterium, halogen atom, hydroxyl group, cyano group, nitro group, amino group, amidino group, hydrazine, hydrazone, carboxyl group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid or salt thereof, C ₁ -C ₆₀ alkyl group (eg For example, methyl group, ethyl group, propyl group, butyl group, pentyl group and the like), C ₂ -C ₆₀ alkenyl group, C ₂ -C ₆₀ alkynyl group and C ₁ -C ₆₀ alkoxy group (for example, methoxy group, ethoxy A phenyl group and a naphthyl group substituted with at least one of a period, a propoxy group, a butoxy group, a pentoxy group, and the like; It may be one of, but is not limited thereto.

As described above, in Formula 1, when R ₅ and R ₆ are connected to each other with a single bond, a linking group of the following Formula 4A, or a linking group of the following Formula 4B, the condensed cyclic compound is represented by the following Formulas 1A to 1D (Formula 1, R ₅ and R ₆ = substituted or unsubstituted phenyl group) may be represented by any one of:

<Formula 1A>

<Formula 1B>

<Formula 1C>

<Formula 1D>

In Formulas 1A to 1D, definitions for R ₁ to R ₄ , Ar ₅ , Ar ₆ , c, d, X ₁ to X ₁₀ and X ₂₁ to X ₂₃ are the same as described above; Z ₂₁ and Z ₂₂ are each independently hydrogen, deuterium, halogen atom, hydroxyl group, cyano group, nitro group, amino group, amidino group, hydrazine, hydrazone, carboxyl group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid Salts thereof, C ₁ -C ₆₀ alkyl groups, C ₂ -C ₆₀ alkenyl groups, C ₂ -C ₆₀ alkynyl groups or C ₁ -C ₆₀ alkoxy groups; u is an integer from 1 to 4; v may be an integer from 1 to 6.

For example, in Formulas 1A to 1D, Z ₂₁ and Z ₂₂ may each independently represent hydrogen, deuterium, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an amino group, an amidino group, a hydrazine, a hydrazone, or a carboxyl group. Salts thereof, sulfonic acid groups or salts thereof, phosphoric acid or salts thereof, methyl groups, ethyl groups, propyl groups, butyl groups, pentyl groups, methoxy groups, ethoxy groups, propoxy groups, butoxy groups, or pentoxy groups, but are not limited thereto. no.

In Formula 1, a combination of one or more of R ₁ and R ₂ and R ₃ and R ₄ may be connected to each other. For example, in Formula 1, at least one of —N (R ₁ ) (R ₂ ) and —N (R ₃ ) (R ₄ ) may be represented by one of Formulas 5A to 5F, but is not limited thereto. no:

In Formulas 5A to 5F, Z ₃₁ to Z ₄₂ are each independently hydrogen, deuterium, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an amino group, an amidino group, a hydrazine, a hydrazone, a carboxyl group, or a salt thereof; Sulfonic acid groups or salts thereof, phosphoric acid or salts thereof, C ₁ -C ₆₀ alkyl groups, C ₂ -C ₆₀ alkenyl groups, C ₂ -C ₆₀ alkynyl groups, C ₁ -C ₆₀ alkoxy groups or C ₅ -C ₆₀ aryl groups; w and x, independently of each other, may be an integer from 1 to 8.

For example, in Formulas 5A to 5F, Z ₃₁ to Z ₄₂ are each independently hydrogen, deuterium, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an amino group, an amidino group, a hydrazine, a hydrazone, or a carboxyl group. Age salts, sulfonic acid groups or salts thereof, phosphoric acid or salts thereof, methyl groups, ethyl groups, propyl groups, butyl groups, pentyl groups, methoxy groups, ethoxy groups, propoxy groups, butoxy groups, pentoxy groups, phenyl groups, naphthyl groups or anthryls It may be, but is not limited to.

For example, in Formula 1, at least one of -N (R ₁ ) (R ₂ ) and -N (R ₃ ) (R ₄ ) may be represented by one of Formulas 6A to 6F, but is not limited thereto. no:

For the description of Z ₃₁ , Z ₃₂ , Z ₃₃ , Z ₃₄ , Z ₃₅ and Z ₄₂ in Formulas 6A to 6F, refer to the above description. For example, Z ₃₁ , Z ₃₂ , Z ₃₃ , Z ₃₄ and Z ₃₅ may be each independently hydrogen or a C ₁ -C ₁₀ alkyl group, and Z42 may be a phenyl group, a naphthyl group, or an anthryl group.

In Formula 1, X ₁ to X ₁₀ are each independently hydrogen, deuterium, halogen atom, hydroxyl group, cyano group, nitro group, amino group, amidino group, hydrazine, hydrazone, carboxyl group or salt thereof, sulfonic acid group or Salts thereof, phosphoric acid or salts thereof, substituted or unsubstituted C ₁ -C ₆₀ alkyl groups, substituted or unsubstituted C ₂ -C ₆₀ alkenyl groups, substituted or unsubstituted C ₂ -C ₆₀ alkynyl groups, substituted or unsubstituted Substituted C ₁ -C ₆₀ alkoxy group, substituted or unsubstituted C ₃ -C ₆₀ cycloalkyl group, substituted or unsubstituted C ₅ -C ₆₀ aryl group, substituted or unsubstituted C ₅ -C ₆₀ aryloxy group, substituted Or an unsubstituted C ₅ -C ₆₀ arylthio group, a substituted or unsubstituted C ₂ -C ₆₀ heteroaryl group, -Si (R ₂₁ ) (R ₂₂ ) (R ₂₃ ) or -N (R ₂₄ ) (R ₂₅₎ provided that, where, R ₂₁ to R ₂₅ are, each independently, a substituted or unsubstituted C ₁ -C ₆₀ alkyl groups to each other, a substituted or unsubstituted C ₂ -C ₆₀ alkenyl group, a substituted or unsubstituted A C ₂ -C ₆₀ alkynyl group, a substituted or unsubstituted C ₁ -C ₆₀ alkoxy group, a substituted or unsubstituted C ₃ -C ₆₀ cycloalkyl group, a substituted or unsubstituted C ₅ -C ₆₀ aryl group, a substituted or It may be an unsubstituted C ₅ -C ₆₀ aryloxy group, a substituted or unsubstituted C ₅ -C ₆₀ arylthio group, or a substituted or unsubstituted C ₂ -C ₆₀ heteroaryl group.

For example, in Formula 1, X ₁ to X ₁₀ independently of each other, hydrogen, deuterium, halogen atom, hydroxyl group, cyano group, nitro group, amino group, amidino group, hydrazine, hydrazone, carboxyl group or its Salt, sulfonic acid group or salt thereof, phosphoric acid or salt thereof, substituted or unsubstituted C ₁ -C ₁₀ alkyl group, substituted or unsubstituted C ₁ -C ₁₀ alkoxy group or substituted or unsubstituted C ₅ -C ₁₄ aryl group have. Two or more adjacent substituents of X ₁ to X ₁₀ may be bonded to each other to form a saturated or unsaturated ring.

According to one embodiment, the condensed cyclic compound may be any one of the following Compounds 1 to 78, but is not limited thereto (TMS = trimethylsilyl):

<Compound 1> <Compound 2> <Compound 3>

<Compound 4> <Compound 5> <Compound 6>

<Compound 7> <Compound 8> <Compound 9>

<Compound 10> <Compound 11> <Compound 12>

<Compound 13> <Compound 14> <Compound 15>

<Compound 16> <Compound 17> <Compound 18>

<Compound 19> <Compound 20> <Compound 21>

<Compound 22> <Compound 23> <Compound 24>

<Compound 25> <Compound 26> <Compound 27>

<Compound 28> <Compound 29> <Compound 30>

<Compound 31> <Compound 32> <Compound 33>

<Compound 34> <Compound 35> <Compound 36>

<Compound 37> <Compound 38> <Compound 39>

<Compound 40> <Compound 41> <Compound 42>

<Compound 43> <Compound 44> <Compound 45>

<Compound 46> <Compound 47> <Compound 48>

<Compound 49> <Compound 50> <Compound 51>

<Compound 52> <Compound 53> <Compound 54>

<Compound 55> <Compound 56> <Compound 57>

<Compound 58> <Compound 59> <Compound 60>

<Compound 61> <Compound 62> <Compound 63>

<Compound 64> <Compound 65> <Compound 66>

<Compound 67> <Compound 68> <Compound 69>

<Compound 70> <Compound 71> <Compound 72>

<Compound 73> <Compound 74> <Compound 75>

<Compound 76> <Compound 77> <Compound 78>

In the present specification, specific examples of the unsubstituted C ₁ -C ₆₀ alkyl group (or C ₁ -C ₆₀ alkyl group) include methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, iso-amyl, hexyl and the like. And a substituted C ₁ -C ₆₀ alkyl group is one or more hydrogen of the unsubstituted C ₁ -C ₆₀ alkyl group, deuterium; A halogen atom; Hydroxyl group; Cyano group; A nitro group; An amino group; Amidino groups; Hydrazine; Hydrazone; Carboxyl groups or salts thereof; Sulfonic acid groups or salts thereof; Phosphoric acid or salts thereof; C ₁ -C ₆₀ alkyl group; C ₂ -C ₆₀ alkenyl group; C ₂ -C ₆₀ alkynyl group; C ₁ -C ₆₀ alkoxy group; C ₃ -C ₆₀ cycloalkyl group; C ₅ -C ₆₀ aryl group; C ₅ -C ₆₀ aryloxy group; C ₅ -C ₆₀ arylthio groups; C ₂ -C ₆₀ heteroaryl group; Deuterium, halogen atom, hydroxyl group, cyano group, nitro group, amino group, amidino group, hydrazine, hydrazone, carboxyl group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid or salt thereof, C ₁ -C ₆₀ alkyl group, C ₂ A C ₁ -C ₆₀ alkyl group, a C ₂ -C ₆₀ alkenyl group, a C ₂ -C ₆₀ alkynyl group substituted with one or more of a —C ₆₀ alkenyl group, a C ₂ -C ₆₀ alkynyl group and a C ₁ -C ₆₀ alkoxy group, C ₁ -C ₆₀ alkoxy group, C ₃ -C ₆₀ cycloalkyl, C ₅ -C ₆₀ aryl group, C ₅ -C ₆₀ aryloxy groups, C ₅ -C ₆₀ aryl Im import and C ₂ -C ₆₀ heteroaryl group, ; -N (Q ₁ ) (Q ₂ ); Or -Si (Q ₃ ) (Q ₄ ) (Q ₅ ); wherein Q ₁ to Q ₅ are each independently a C ₃ -C ₆₀ cycloalkyl group, a C ₅ -C ₆₀ aryl group; C ₅ -C ₆₀ aryloxy group; C ₅ -C ₆₀ arylthio group; C ₂ -C ₆₀ heteroaryl group; and deuterium, halogen atom, hydroxyl group, cyano group, nitro group, amino group, amidino group, hydrazine , Hydrazone, carboxyl group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid or salt thereof, C ₁ -C ₆₀ alkyl group, C ₂ -C ₆₀ alkenyl group, C ₂ -C ₆₀ alkynyl group and C ₁ -C ₆₀ alkoxy group One or more substituted C ₁ -C ₆₀ alkyl groups, C ₂ -C ₆₀ alkenyl groups, C ₂ -C ₆₀ alkynyl groups, C ₁ -C ₆₀ alkoxy groups, C ₃ -C ₆₀ cycloalkyl groups, C ₅ -C ₆₀ aryl group, C ₅ -C ₆₀ aryloxy groups, C ₅ -C ₆₀ aryl Im import and C ₂ -C ₆₀ heteroaryl group; one).

Unsubstituted C ₁ -C ₆₀ alkoxy group (or C ₁ -C ₆₀ alkoxy group) in the present specification has the formula of -OA (where A is an unsubstituted C ₁ -C ₆₀ alkyl group as described above). And specific examples thereof include methoxy, ethoxy, isopropyloxy, and the like, and at least one hydrogen atom of these alkoxy groups may be substituted with the same substituent as in the case of the substituted C ₁ -C ₆₀ alkyl group described above. .

In this specification, an unsubstituted C ₂ -C ₆₀ alkenyl group (or a C ₂ -C ₆₀ alkenyl group) includes one or more carbon double bonds in the middle or the end of the unsubstituted C ₂ -C ₆₀ alkyl group. it means. Examples are ethenyl, propenyl, butenyl and the like. At least one hydrogen atom of these unsubstituted C ₂ -C ₆₀ alkenyl groups may be substituted with the same substituent as in the case of the substituted C ₁ -C ₆₀ alkyl group described above.

An unsubstituted C ₂ -C ₆₀ alkynyl group (or C ₂ -C ₆₀ alkynyl group) herein includes one or more carbon triple bonds in the middle or at the end of the C ₂ -C ₆₀ alkyl group as defined above. Means that. Examples include ethynyl, propynyl, and the like. At least one hydrogen atom of these alkynyl groups may be substituted with the same substituent as in the case of the substituted C ₁ -C ₆₀ alkyl group described above.

As used herein, an unsubstituted C ₅ -C ₆₀ aryl group refers to a monovalent group having a carbocyclic aromatic system having 5 to 60 carbon atoms containing at least one aromatic ring, and unsubstituted C _5- C ₆₀ arylene group refers to a divalent group having a carbocyclic aromatic system having 5 to 60 carbon atoms containing at least one aromatic ring. When the aryl group and the arylene group include two or more rings, the two or more rings may be fused to each other. At least one hydrogen atom of the aryl group and the arylene group may be substituted with the same substituent as the substituted C ₁ -C ₆₀ alkyl group described above.

Examples of the substituted or unsubstituted C ₅ -C ₆₀ aryl group include a phenyl group, a C ₁ -C ₁₀ alkylphenyl group (eg, ethylphenyl group), a C ₁ -C ₁₀ alkylbiphenyl group (eg, ethylbiphenyl group ), Halophenyl groups (e.g., o-, m- and p-fluorophenyl groups, dichlorophenyl groups), dicyanophenyl groups, trifluoromethoxyphenyl groups, o-, m-, and p-tolyl groups, o-, m- and p-cumenyl groups, mesityl groups, phenoxyphenyl groups, (α, α-dimethylbenzene) phenyl groups, (N, N'-dimethyl) aminophenyl groups, (N, N'-diphenyl) aminophenyl groups, penteres Neyl group, indenyl group, naphthyl group, halonaphthyl group (e.g. fluoronaphthyl group), C ₁ -C ₁₀ alkylnaphthyl group (e.g. methylnaphthyl group), C ₁ -C ₁₀ alkoxynaphthyl group (e.g. For example, methoxynaphthyl group), anthracenyl group, azurenyl group, heptarenyl group, acenaphthylenyl group, phenenalenyl group, fluorenyl group, anthraquinolyl group, methyl anthryl group, phenanthryl group, triphenyle Nilyl, pyrenyl , Cryenyl, ethyl-crisenyl, pisenyl, peryleneyl, chloroperylenyl, pentaphenyl, pentasenyl, tetraphenylenyl, hexaphenyl, hexasenyl, rubisenyl, coroneyl , Trinaphthylenyl group, heptaphenyl group, heptasenyl group, pyrantrenyl group, obarenyl group, and the like, and examples of the substituted C ₅ -C ₆₀ aryl group include the unsubstituted C ₅ -C ₆₀ as described above. It can be easily recognized with reference to the example of an aryl group and the substituent of the substituted C ₁ -C ₆₀ alkyl group. Examples of the substituted or unsubstituted C ₅ -C ₆₀ arylene group may be easily recognized with reference to the examples of the substituted or unsubstituted C ₅ -C ₆₀ aryl group.

As used herein, an unsubstituted C ₂ -C ₆₀ heteroaryl group refers to a monovalent group having 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 being C And an unsubstituted C ₂ -C ₆₀ heteroarylene group means a divalent group having 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 being C do. Here, when the heteroaryl group and heteroarylene group includes two or more rings, two or more rings may be fused to each other. At least one hydrogen atom of the heteroaryl group and the heteroarylene group may be substituted with the same substituent as in the case of the C ₁ -C ₆₀ alkyl group described above.

Examples of the unsubstituted C ₂ -C ₆₀ heteroaryl group, pyrazolyl group, imidazolyl group, oxazolyl group, thiazolyl group, triazolyl group, tetrazolyl group, oxadiazolyl group, pyridinyl group, pyri A diginyl group, a pyrimidinyl group, a triazinyl group, a carbazolyl group, an indolyl group, a quinolinyl group, an isoquinolinyl group, a benzimidazolyl group, an imidazopyridinyl group, an imidazopyrimidinyl group, etc. are mentioned. Examples of the unsubstituted C ₂ -C ₆₀ hetero arylene groups may be easily recognized with reference to the examples of the substituted or unsubstituted C ₂ -C ₆₀ arylene group.

The substituted or unsubstituted C ₅ -C ₆₀ aryloxy group refers to -OA ₂ , wherein A ₂ is the substituted or unsubstituted C ₅ -C ₆₀ aryl group, and the substituted or unsubstituted C ₅ -C ₆₀ arylthio refers to -SA ₃ , wherein A ₃ is the substituted or unsubstituted C ₅ -C ₆₀ aryl group.

The condensed cyclic compound having Formula 1 may be synthesized using a known organic synthesis method. Synthesis method of the condensed cyclic compound can be easily recognized by those skilled in the art with reference to the following examples.

The condensed cyclic compound represented by Formula 1 as described above may have excellent heat resistance and luminescence properties. Specifically, the carbon of the A position and the carbon of the B position of the formula (1), optionally with Ar ₅ and Ar ₆ between, -N (R ₁ ) (R ₂ ) and -N (R ₃ ) (R ₄ ) Combined with.

In general, when the conjugation length of the main body condensed ring is longer, the band gap becomes smaller and the light emission wavelength is shifted toward the longer wavelength. The C position may form a wider bandgap than the structure leading to the conjugation as the conjugation is broken. Therefore, the condensed cyclic compound may be usefully used as a blue light emitting material due to a wide bandgap effect due to an appropriate conjugation state.

&Lt; Formula 1 >

When driving the organic light emitting device employing such a condensed cyclic compound between a pair of electrodes (anode and cathode), the condensed cyclic compound is generated in the organic layer between the pair of electrodes, between the organic layers or between the organic layer and the electrode. Since the organic light emitting device employing the condensed cyclic compound may have excellent driving voltage, efficiency, brightness, and lifespan.

The condensed cyclic compound of Formula 1 may be used between a pair of electrodes of the organic light emitting device. For example, the condensed cyclic compound may be used as a light emitting material, but is not limited thereto.

Accordingly, a condensed cyclic compound represented by Chemical Formula 1 including a first electrode, a second electrode facing the first electrode, and an organic layer interposed between the first electrode and the second electrode, wherein the organic layer is An organic light emitting device is provided.

The condensed cyclic compound may be included in the organic layer in the form of a single material or a combination of different materials. For example, the organic light emitting device of Example 1 to be described later includes only Compound 1 (which serves as a blue dopant) as a condensed cyclic compound in the form of a single material. Alternatively, for example, the light emitting layer of the organic light emitting device may include various combinations of Compounds 1 and 3 (which serve as blue dopants) as the condensed cyclic compound. In the present specification, the expression "the organic layer includes the condensed cyclic compound in the form of a single material or a mixture of different materials" may be easily understood by those skilled in the art with reference to the above description.

The organic layer has a hole injection layer, a hole transport layer, a hole injection function and a hole transport function at the same time, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer and an electron transport function and an electron injection function at the same time It may include at least one of the functional layer.

For example, the organic layer,

1) hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer; or

2) a functional layer / light emitting layer / electron transport layer / electron injection layer having a hole injection function and a hole transport function at the same time;

It may have a structure of, but is not limited thereto.

As used herein, the term "organic layer" refers to a single layer or a plurality of layers interposed between the first electrode and the second electrode in the organic light emitting device, and may include a metal complex and the like in addition to the organic material.

For example, the organic layer may include a light emitting layer, and the condensed cyclic compound may be present in the light emitting layer. That is, the condensed cyclic compound may be used as a light emitting material. In this case, the emission layer may further include a host, and the condensed cyclic compound included in the emission layer may serve as a dopant.

The light emitting layer may be a red, green or blue light emitting layer. For example, the light emitting layer may be a blue light emitting layer. In this case, the condensed cyclic compound may be used as a blue dopant to provide an organic light emitting device having high efficiency, high brightness, high color purity, and long life.

1 is a schematic cross-sectional view of an organic light emitting device according to an embodiment of the present invention. Hereinafter, a structure and a manufacturing method of an organic light emitting diode according to an embodiment of the present invention will be described with reference to FIG. 1. The organic light emitting diode includes a substrate 10, a first electrode 20, a hole injection layer 30, a hole transport layer 40, a light emitting layer 50, an electron transport layer 60, an electron injection layer 70, and a second. The electrode 80 is provided in order.

First, as the substrate 10, a substrate used in a conventional organic light emitting device may be used, and a glass substrate or a transparent plastic substrate having excellent mechanical strength, thermal stability, transparency, surface smoothness, ease of handling, and water resistance may be used. have.

The first electrode 20 may be formed by using a deposition method, a sputtering method, or the like for the first electrode material on the substrate. When the first electrode 20 is an anode, the material for the first electrode may be selected from materials having a high work function to facilitate hole injection. The first electrode 20 may be a reflective electrode or a transmissive electrode. Indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO 2), zinc oxide (ZnO) and the like may be used as the first electrode material. Alternatively, when magnesium (Mg), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag), etc. are used, One electrode 20 may be formed as a reflective electrode.

Various modifications are possible, such as the first electrode 20 may have a single layer or a multilayer structure of two or more.

The organic layer including the hole injection layer 30, the hole transport layer 40, the light emitting layer 50, the electron transport layer 60, and the electron injection layer 70 is formed on the first electrode 20.

The hole injection layer 30 may be formed on the first electrode 20 using various methods such as vacuum deposition, spin coating, casting, and LB.

When the hole injection layer 30 is formed by the vacuum deposition method, the deposition conditions vary depending on the compound used as the material of the hole injection layer 30, the structure and thermal characteristics of the hole injection layer 30, and the like. For example, the deposition temperature may be selected from a range of about 100 to about 500 ° C., a vacuum degree of about 10 ⁻⁸ to about 10 ⁻³ torr, and a deposition rate of about 0.01 to about 100 μs / sec, but is not limited thereto.

When the hole injection layer 30 is formed by spin coating, the coating conditions differ depending on the compound used as the material of the hole injection layer 30, the structure and the thermal characteristics of the desired hole injection layer 30. However, the coating speed of about 2000rpm to about 5000rpm, the heat treatment temperature for removing the solvent after coating may be selected from a temperature range of about 80 ℃ to 200 ℃, but is not limited thereto.

A well-known hole injecting material can be used as the hole injecting material, for example, N, N'-diphenyl-N, N'-bis- [4- (phenyl-m- Tolyl-amino) -phenyl] -biphenyl-4,4′-diamine (N, N′-diphenyl-N, N′-bis- [4- (phenyl-m-tolyl-amino) -phenyl] -biphenyl- Phthalocyanine compounds such as 4,4′-diamine: DNTPD), copper phthalocyanine (CuPc), m-MTDATA [4,4 ', 4' '-tris (3-methylphenylphenylamino) triphenylamine], TDATA, 2-TNATA, Pani / DBSA (Polyaniline / Dodecylbenzenesulfonic acid: polyaniline / dodecylbenzenesulfonic acid), PEDOT / PSS (Poly (3,4-ethylenedioxythiophene) / Poly (4-styrenesulfonate): poly (3,4-ethylenedioxythiophene) / poly (4 Styrenesulfonate)), Pani / CSA (Polyaniline / Camphor sulfonicacid: polyaniline / camphorsulfonic acid) or PANI / PSS (Polyaniline) / Poly (4-styrenesulfonate): polyaniline) / poly (4-styrenesulfonate)) Can be used, but is not limited thereto.

The hole injection layer 30 may have a thickness of about 100 kPa to about 10000 kPa, for example, about 100 kPa to about 1000 kPa. When the thickness of the hole injection layer 30 satisfies the aforementioned range, a satisfactory hole injection characteristic may be obtained without a substantial increase in driving voltage.

Next, the hole transport layer 40 may be formed on the hole injection layer 30 using various methods such as vacuum deposition, spin coating, cast, and LB. In the case of forming the hole transport layer 40 by vacuum deposition and spinning, the deposition conditions and coating conditions vary depending on the compound used, but in general, the hole transport layer 40 may be selected from a range of conditions substantially the same as the formation of the hole injection layer 30. have.

As the hole transporting material, a known hole transporting material can be used. As a known hole transport material, for example, carbazole derivatives such as N-phenylcarbazole and polyvinylcarbazole, N, N'-bis (3-methylphenyl) -N, N'-diphenyl- [1 , 1-biphenyl] -4,4'-diamine (TPD), TCTA (4,4 ', 4 "-tris (N-carbazolyl) triphenylamine (4,4', 4" -tris (N- carbazolyl) triphenylamine)), NPD (N, N'-di-1-naphthyl-N, N'-diphenyl-1,1'-

biphenyl-4,4'diamine) and the like, but is not limited thereto.

The hole transport layer 40 may have a thickness of about 50 kPa to about 2000 kPa, for example, about 100 kPa to about 1500 kPa. When the thickness of the hole transport layer 40 satisfies the above-described range, a satisfactory hole transport characteristic may be obtained without a substantial increase in driving voltage.

Alternatively, instead of the hole injection layer and the hole transport layer described above, a functional layer having a hole injection function and a hole transport function can be formed at the same time. The functional layer material having the hole injection function and the hole transport function at the same time may be selected from known materials.

At least one of the hole injection layer, the hole transport layer, and a functional layer having a hole injection function and a hole transport function at the same time may be a known hole injection material, a known hole transport material and / or a hole injection function, and a hole transport function as described above. In addition to the material having at the same time, it may further include a charge-generating material to improve the conductivity of the film.

The charge-generating material may be, for example, a p-dopant. Non-limiting examples of the p-dopant include tetracyanoquinonedimethane (TCNQ) and 2,3,5,6-tetrafluoro-tetracyano-1,4-benzoquinonedimethane (F4TCNQ) Quinone derivatives such as these; Metal oxides such as tungsten oxide and molybdenum oxide; And cyano group-containing compounds such as Compound 200, and the like, but are not limited thereto.

<Compound 200>

When the hole injection layer, the hole transport layer, or the functional layer having the hole injection function and the hole transport function at the same time further include the charge-generating material, the charge-generating material is homogeneously dispersed in the layers or Various modifications are possible, such as, or may be unevenly distributed.

The light emitting layer 50 is formed on the hole transport layer 40 (or a functional layer having a hole injection function and a hole transport function at the same time) by using a method such as vacuum deposition, spin coating, cast, LB, or the like. can do. In the case of forming the light emitting layer 50 by vacuum deposition and spin coating, the deposition conditions vary depending on the compound used, and in general, may be selected from a range of conditions substantially the same as the formation of the hole injection layer 30.

As the light emitting layer material, at least one of a condensed cyclic compound of Formula 1 and / or a known light emitting material (host and / or dopant) may be used. For example, the emission layer may include a known host, and may include a condensed cyclic compound represented by Formula 1 as a dopant. Here, the condensed cyclic compound may serve as a blue dopant.

Examples of known hosts include Alq ₃ , CBP (4,4'-N, N'-dicarbazole-biphenyl), PVK (poly (n-vinylcarbazole)), 9,10-di (naphthalene-2- I) anthracene (ADN), TCTA, TPBI (1,3,5-tris (N-phenylbenzimidazol-2-yl) benzene (1,3,5-tris (N-phenylbenzimidazole-2-yl) benzene) ), TBADN (3-tert-butyl-9,10-di (naphth-2-yl) anthracene), E3, DSA (distyrylarylene) and the like can be used, but is not limited thereto.

PVK ADN

Alternatively, the host may be an anthracene-based compound represented by Formula 60:

<Formula 60>

In Formula 60, Ar ₁₁ and Ar ₁₂ are each independently a substituted or unsubstituted C ₅ -C ₆₀ arylene group; Ar ₁₃ and Ar ₁₄ are each independently a substituted or unsubstituted C ₁ -C ₁₀ alkyl group or a substituted or unsubstituted C ₅ -C ₆₀ aryl group; e and f may be an integer of 0 to 5 independently of each other.

For example, in Formula 60, Ar ₁₁ and Ar ₁₂ may be a phenylene group; Or a phenylene group substituted with at least one of a phenyl group, a naphthyl group, and an anthryl group, but is not limited thereto.

In Formula 60, e and f may be each independently 0, 1 or 2.

In Formula 60, Ar ₁₃ and Ar ₁₄ are each independently a C ₁ -C ₁₀ alkyl group substituted with one or more of a phenyl group, a naphthyl group, and an anthryl group; Phenyl group; Naphthyl group; Anthryl group; Pyrenyl group; Phenanthrenyl group; And deuterium, halogen atom, hydroxyl group, cyano group, nitro group, amino group, amidino group, hydrazine, hydrazone, carboxyl group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid or salt thereof, C ₁ -C ₆₀ alkyl group, C Phenyl, naphthyl, anthryl, pyrenyl and phenanthrenyl groups substituted with one or more of ₂ -C ₆₀ alkenyl, C ₂ -C ₆₀ alkynyl and C ₁ -C ₆₀ alkoxy groups; It may be one of, but is not limited thereto.

For example, in Formula 60, Ar ₁₁ and Ar ₁₂ may be a phenylene group; Or a phenylene group substituted with one or more of a phenyl group, a naphthyl group and an anthryl group, and e and f are each independently 0, 1 or 2; Ar ₁₃ and Ar ₁₄ are each independently a C ₁ -C ₁₀ alkyl group substituted with one or more of a phenyl group, a naphthyl group and an anthryl group; Phenyl group; Naphthyl group; Anthryl group; Pyrenyl group; And phenanthrenyl group; It may be one of, but is not limited thereto.

For example, the anthracene-based compound represented by Formula 60 may be one of the following compounds BH1 to BH39, but is not limited thereto.

BH01 BH02 BH03 BH04

BH05 BH06 BH07 BH08

BH09 BH10 BH11 BH12

BH13 BH14 BH15 BH16

BH17 BH18 BH19 BH20

BH21 BH22 BH23 BH24

BH25 BH26 BH27 BH28

BH29 BH30 BH31 BH32

BH33 BH34 BH35 BH36

BH37 BH38 BH39

Meanwhile, in order to form a full color organic light emitting device, the red light emitting layer and the green light emitting layer may be further patterned.

In this case, PtOEP, Ir (piq) ₃ , Btp ₂ Ir (acac), or the like may be used as a known red dopant, but 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.

C545T

The content of the dopant in the light emitting layer 50 may be generally selected from about 0.01 to about 15 parts by weight based on about 100 parts by weight of the host, but is not limited thereto.

The emission layer 50 may have a thickness of about 100 kPa to about 1000 kPa, for example, about 200 kPa to about 600 kPa. When the thickness of the light emitting layer 50 satisfies the aforementioned range, the light emitting layer 50 may exhibit excellent light emission characteristics without a substantial increase in driving voltage.

Next, the electron transport layer 60 is formed using various methods such as vacuum deposition, spin coating, casting, or the like. In the case of forming the electron transporting layer 60 by vacuum deposition and spin coating, the conditions vary depending on the compound used, and in general, the electron transport layer 60 may be selected from a condition range substantially the same as the formation of the hole injection layer 30. As the electron transport layer material, a known electron transport material may be used as a function of stably transporting electrons injected from an electron injection electrode (Cathode). Examples of known electron transport materials include quinoline derivatives, in particular tris (8-quinolinorate) aluminum (Alq 3), TAZ, Balq, beryllium bis (benzoquinolin-10-noate) olate: Bebq ₂ ), ADN, compound 201, compound 202 and the like may be used, but is not limited thereto.

<Compound 201> <Compound 202>

The electron transport layer 60 may have a thickness of about 100 kPa to about 1000 kPa, for example, about 150 kPa to about 500 kPa. When the thickness of the electron transport layer 60 satisfies the aforementioned range, a satisfactory electron transport characteristic may be obtained without a substantial increase in driving voltage.

Alternatively, the electron transport layer 60 may further include a metal-containing material in addition to the known electron transport organic compound as described above.

The metal-containing material may comprise a Li complex. Non-limiting examples of the Li complex include lithium quinolate (LiQ) or the following compound 203:

Compound 203

In addition, an electron injection layer 70, which is a material having a function of facilitating injection of electrons from the cathode, may be stacked on the electron transport layer 60, which does not particularly limit the material.

As the electron injection layer forming material, any material known as an electron injection layer forming material such as LiF, NaCl, CsF, Li ₂ O, BaO, or the like may be used. Although the deposition conditions of the electron injection layer vary depending on the compound used, they may be generally selected from the same range of conditions as the formation of the hole injection layer.

The electron injection layer 70 may have a thickness of about 1 kPa to about 100 kPa and about 3 kPa to about 90 kPa. When the thickness of the electron injection layer 70 satisfies the above range, a satisfactory electron injection characteristic may be obtained without a substantial increase in driving voltage.

The second electrode 80 is provided on the electron injection layer 70. The second electrode 80 may be a cathode, which is an electron injection electrode. In this case, as the metal for forming the second electrode, a metal, an alloy, an electrically conductive compound having a low work function, and a mixture thereof may be used. Can be. Specific examples include lithium (Li), magnesium (Mg), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag), and the like. It can be formed into a thin film to obtain a transmissive electrode. On the other hand, various modifications are possible, such as to form a transmissive electrode using ITO and IZO to obtain a front light emitting device.

The organic light emitting device may be used in a display device and a monochrome or white lighting device. The display device and the lighting device may further include one or more thin film transistors, and the first electrode of the organic light emitting device may contact one of the source and drain electrodes included in the thin film transistor.

Hereinafter, the organic light emitting device according to one embodiment of the present invention, for example, synthesis examples and examples will be described in more detail, but the present invention is not limited to the following synthesis examples and examples.

 [Example]

Synthetic example  1: Synthesis of Compound 1

Synthetic example  1- (1): Synthesis of Intermediate 1-a

According to Scheme 1, intermediate 1-a was synthesized:

<Reaction Scheme 1>

                                                            Intermediate 1-a

50 g (194 mmol) of 9-bromo phenanthrene was put into a round bottom flask containing 500 ml of tetrahydrofuran, and the temperature was adjusted to -78 ° C under a nitrogen atmosphere. After 30 minutes, 146 ml (233 mmol) of normal butyllithium was slowly added dropwise, and after 1 hour, 28.3 g (274 mmol) of trimethyl borate was slowly added dropwise, and the temperature was raised to room temperature. After stirring for about 12 hours at room temperature, 2N (normal) hydrochloric acid aqueous solution was added dropwise to the reaction solution until the acid, extracted, and the organic layer was collected and distilled under reduced pressure. Recrystallization with normal nucleic acid, followed by filtration and drying yielded intermediate 1-a (35 g, yield 81%) as a white solid.

Synthetic example  1- (2): Synthesis of Intermediate 1-b

Intermediate 1-b was synthesized according to Scheme 2:

<Reaction Scheme 2>

                                                               Intermediate 1-b

24 g (112 mmol) of methyl 2-bromobenzoate, 34.7 g (0.156 mmol) of Intermediate 1-a, tetrakistriphenylphosphinepalladium {Pd (PPh ₃ ) ₄ } 2.6 g (2 mmol), carbonated 30.9 g (223 mmol) of potassium, 50 mL of water, 125 ml of toluene and 125 mL of tetrahydrofuran were added thereto, and the mixture was refluxed for 12 hours. After completion of the reaction, the reactants were separated by layer, the organic layer was concentrated under reduced pressure, dried over a column, and the intermediate 1-b (25 g, yield 72%) was obtained as a white solid.

Synthetic example  1- (3): Synthesis of Intermediate 1-c

According to Scheme 3, intermediate 1-c was synthesized:

<Reaction Scheme 3>

                                                        Intermediate 1-c

After putting 25 g (80 mmol) of the intermediate 1-b into a round bottom flask containing 250 ml of tetrahydrofuran, the temperature was lowered to −78 ° C. under a nitrogen atmosphere. After 30 minutes, 150 ml (240 mmol) of 1.6 M phenyllithium was slowly added dropwise, and the temperature was raised to room temperature after 1 hour. After stirring at room temperature for about 2 hours, an aqueous solution of ammonium chloride was added dropwise, followed by extraction. The organic layers were collected and distilled under reduced pressure. After recrystallization with normal nucleic acid and the filter was dried to give an intermediate 1-c (29g, 83% yield) as a white solid.

Synthetic example  1- (4): Synthesis of Intermediate 1-d

Intermediate 1-d was synthesized according to Scheme 4 below:

<Reaction Scheme 4>

                                                        Intermediate 1-d

29 g (66 mmol) of Intermediate 1-c was placed in a round bottom flask containing 290 ml of acetic acid. Thereafter, after the temperature was raised to 80 ° C., 1-2 drops of aqueous hydrochloric acid solution were added, refluxed for about 2 hours, and the temperature was adjusted to room temperature. As a result of filtering the solid produced therefrom, the white solid of intermediate 1-d (27 g, yield 93%) as a white solid was measured.

Synthetic example  1- (5): Synthesis of Intermediate 1-e

Intermediate 1-e was synthesized according to Scheme 5 below:

Scheme 5

                                                  Intermediate 1-e

An intermediate 1-d 27g (65 mmol) was added to a round bottom flask containing 216 ml of chloroform, followed by stirring. After diluting 28.9 g (181 mmol) of bromine with 54 ml of chloroform, it was slowly added dropwise and stirred at room temperature for 48 hours. The resulting solid was filtered and dried to yield intermediate 1-e (27 g, 93% yield) as a white solid.

Synthetic example  1- (6): Synthesis of Compound 1

Compound 1 was synthesized according to Scheme 7:

<Reaction Scheme 7>

                                                             Compound 1

10 g (17 mmol) of intermediate 1-e, 7.6 g (45 mmol) of diphenylamine, 0.2 g (0.7 mmol) of palladium acetate {Pd (OAc) ₂ }, 6.7 g (69 mmol) of sodium tertiary butoxide in a round bottom flask , Tritary butylphosphine 0.14 g (0.7 mmol) and toluene 100ml were added and reacted for 2 hours at a reaction temperature of 100 ℃. After the reaction was completed, the filtrate was concentrated after the filter and separated by column chromatography. The solid produced by recrystallization with toluene and methanol was filtered and dried to give Compound 1 (5.7 g, pale yellow solid, yield 40%).

MS: m / z 752 [M] ⁺

¹ H NMR (CDCl ₃ ) δ 8.89 (d, 1H), 8.47 (d, 1H), 8.40 (s, 1H), 8.24 (d, 1H), 7.73 (t, 1H), 7.63 (m, 2H), 7.27 (m, 23H), 7.01 (m, 10H)

Synthetic example  2: synthesis of compound 3

Synthetic example  2- (1): Synthesis of Intermediate 2-a

Intermediate 2-a was synthesized according to Scheme 8 below:

<Reaction Scheme 8>

                                                              Intermediate 2-a

16.3 g (96 mmol) of 4-amino biphenyl, 15.8 g (101 mmol) of bromobenzene, 0.32 g (1.4 mmol) of palladium acetate, 2,2-bis diphenylphosphino-1,1'- in a round bottom flask 0.9 g (1.4 mmol) of binaphthyl, 18.5 g (193 mmol) of sodium tert-butoxide and 160 ml of toluene were added and refluxed for 24 hours. After controlling the temperature to room temperature, the filtrate was concentrated by filtration and separated by column chromatography. Thereafter, the mixture was recrystallized from dichloromethane and methanol, filtered and dried to obtain intermediate 2-a (15 g, yield 60%) as a white solid.

Synthetic example  2- (2): Synthesis of Compound 3

Compound 3 (3.7 g, pale yellow solid, yield 31%) using the same method as Synthesis Example 1- (6), except that Intermediate 2-a was used instead of diphenyl amine in Synthesis Example 1- (6). ) Was obtained.

MS: m / z 904 [M] ⁺

¹ H NMR (CDCl ₃ ) δ 8.90 (d, 1H), 8.51 (m, 2H), 8.27 (d, 1H), 7.75 (t, 2H), 7.61 (m, 6H), 7.48 (m, 9H), 7.36 (m, 9H), 7.23 (m, 11H), 7.12 (m, 7H)

Synthetic example  3: Synthesis of Compound 9

Synthesis Example 2- (1) except that 4-tert-butylaniline was used instead of 4-amino biphenyl and 1-bromo-4-tert-butylbenzene was used instead of bromo benzene. Using the same method as 2, compound 9 (4.7 g, pale yellow solid, yield 39%) was obtained.

MS: m / z 977 [M] ⁺

¹ H NMR (CDCl ₃ ) δ 8.89 (s, 1H), 8.49 (d, 1H), 8.23 (s, 1H), 7.68 (m, 3H), 7.31 (m, 21H), 7.05 (m, 9H), 1.38 (s, 18H), 1.37 (s, 18H)

Synthetic example  4: Synthesis of Compound 10

Synthesis Example 2- (1) The same method as in Synthesis Example 2 was used except that 4-tert-butylaniline was used instead of 4-amino biphenyl and bromo benzene-d ₅ was used instead of bromo benzene. Compound 10 (2.7 g, pale yellow solid, yield 24%) was obtained.

MS: m / z 875 [M] ⁺

¹ H NMR (CDCl ₃ ) δ 8.91 (d, 1H), 8.45 (m, 2H), 8.26 (d, 1H), 7.67 (m, 3H), 7.30 (m, 15H), 7.07 (m, 6H)

Synthetic example  5: Synthesis of Compound 11

Synthesis Example 2- (1) except that 4-tert-butylaniline was used instead of 4-amino biphenyl and 1-bromo-4- (trimethylsilyl) benzene was used instead of bromo benzene. Using the same method as 2, compound 11 (6.4 g, pale yellow solid, yield 67%) was obtained.

MS: m / z 1009 [M] ⁺

¹ H NMR (CDCl ₃ ) δ 8.88 (d, 1H), 8.51 (d, 1H), 8.43 (S, 1H), 8.24 (d, 1H), 7.73 (t, 1H), 7.64 (m, 2H), 7.21 (m, 29H), 1.36 (s, 9H), 1.35 (S, 9H), 0.30 (s, 9H), 0.29 (s, 9H)

Synthetic example  6: Synthesis of Compound 12

Compound 12 (5.1 g) in the same manner as in Synthesis Example 2, except that 1-bromo-4-tert-butylbenzene was used instead of bromo benzene in Synthesis Example 2- (1). , Pale yellow solid, yield 49%) was obtained.

MS: m / z 1017 [M] ⁺

¹ H NMR (CDCl ₃ ) δ 8.93 (s, 1H), 8.50 (m, 2H), 8.29 (d, 1H), 7.40 (m, 42H), 1.41 (s, 9H), 1.40 (s, 9H)

Synthetic example  7: Synthesis of Compound 28

Except for using methyl magnesium bromide instead of phenyl lithium in Synthesis Example 1- (3) using the same method as in Synthesis Example 1 to obtain Compound 28 (3.3 g, pale yellow solid, yield 38%) as a light yellow solid. It was.

MS: m / z 628 [M] ⁺

¹ H NMR (CDCl ₃ ) δ 8.84 (s, 1H), 8.53 (m, 2H), 8.26 (s, 2H), 7.42 (m, 25H), 1.75 (s, 6H)

Synthetic example  8: Synthesis of Compound 29

In the same manner as in Synthesis Example 1, except that methyl magnesium bromide was used instead of phenyl lithium in Synthesis Example 1- (3) and intermediate 2-a was used instead of diphenyl amine in Synthesis Example 1- (6). Compound 29 (3.3 g, light yellow solid, 38% yield) was obtained.

MS: m / z 780 [M] ⁺

¹ H NMR (CDCl ₃ ) δ 8.85 (s, 1H), 8.55 (m, 2H), 8.28 (s, 2H), 7.47 (m, 33H), 1.76 (s, 6H)

Synthetic example  9: Synthesis of Compound 14

Synthetic example  9- (1): Synthesis of Intermediate 9-a

Intermediate 9-a was synthesized according to Scheme 9 below:

<Reaction Scheme 9>

                                                      Intermediate 9-a

30 g (111.56 mmol) of 2,4-dibromo-6-fluoroaniline, 31.2 g (245.44 mmol) of phenylboronic acid-d ₅ , 61.9 g (446.27 mmol) of potassium carbonate, tetrakistriphenyl in a 1 L round bottom flask 2.6 g (2.20 mmol) of phosphine palladium, 120 mL of water, 300 mL of toluene and 300 mL of tetrahydrofuran were added thereto, and reacted at a reaction temperature of 80 ° C. for 24 hours. After the reaction was completed, the resultant of the reaction was separated into layers to remove the aqueous layer, and the organic layer was separated and concentrated under reduced pressure. Then, the solid obtained by column chromatography using hexane and dichloromethane as a developing solvent was dried and dried. Intermediate 9-a (24.2 g yield 79.4%) was obtained.

Synthetic example  9- (2): Synthesis of Intermediate 9-b

Intermediate 9-b was synthesized according to Scheme 10 below:

<Scheme 10->

                                                       Intermediate 9-b

Intermediate 9-b 15g (55 mmol), bromobenzene-d _{5 in} round bottom flask 8.9 g (55 mmol), 0.25 g (1.1 mmol) palladium acetate, 0.68 g (1.1 mmol) 2,2-bis diphenylphosphino-1,1'-binafryl, 10.6 g (110 mmol) sodium tert-butoxide And 150 ml of toluene were added and refluxed for 24 hours. The filtrate was concentrated by filtration and separated by column chromatography. Thereafter, the mixture was recrystallized from dichloromethane and methanol, filtered and dried to obtain intermediate 9-b (14 g, 72% yield) as a white solid.

Synthesis Example 9 -(3): synthesis of compound 14

Compound 14 (3.1 g, pale yellow solid, yield 24%) using the same method as Synthesis Example 1, except that Intermediate 9-b was used instead of diphenylamine in Synthesis Example 1- (6). Obtained.

Compound 14 (3.1 g, pale yellow solid, yield 24%) was obtained using the same method as Synthesis Example 1-6.

MS: m / z 1123 [M] ⁺

¹ H NMR (CDCl ₃ ) δ 8.81 (s, 1H), 8.35 (d, 1H), 8.05 (s, 2H), 7.71 (t, 2H), 7.34 (m, 16H), 6.84 (d, 2H)

Synthetic example  10: Synthesis of Compound 17

Compound 17 (4.3 g, pale yellow solid, yield) using the same method as in Synthesis Example 2, except that 3-cyanoaniline was used instead of 4-amino biphenyl in Synthesis Example 2- (1). 42%) was obtained.

MS: m / z 803 [M] ⁺

¹ H NMR (CDCl ₃ ) δ 8.90 (d, 1H), 8.51 (m, 2H), 8.33 (d, 1H), 7.74 (m, 3H), 7.25 (m, 29H), 6.93 (d, 2H)

Synthetic example  11: Synthesis of Compound 22

Synthetic example  11- (1): Synthesis of Intermediate 11-a

Intermediate 11-a was synthesized according to Scheme 11 below:

<Reaction Scheme 11>

                                Intermediate 11-a

50 g (197 mmol) of intermediate 1,3-dibromo-5-fluorobenzene, 28.8 (167 mmol) of intermediate 1-naphthyl boronic acid, 4.6 g (3.9 mmol) of tetrakistriphenylphosphinepalladium, potassium carbonate 54.4 g (394 mmol), 450 ml of toluene and 150 ml of water were added and refluxed. When the reaction was completed, the mixture was extracted and distilled under reduced pressure, and the organic layer was separated by column chromatography to obtain a transparent liquid intermediate 11-a (25 g, yield 42%).

Synthetic example  11- (2): Synthesis of Intermediate 11-b

Intermediate 11-b was synthesized according to Scheme 12 below:

<Reaction Scheme 12>

                                                            Intermediate 11-b

Intermediate 11-b was synthesized in the same manner except for using 4-tert-butylaniline instead of 4-amino biphenyl and intermediate 15-a instead of bromobenzene.

Synthetic example  11- (3): Synthesis of Compound 22

Compound 22 (1.6 g, pale yellow solid, yield 21%) using the same method as Synthesis Example 1, except that Intermediate 11-b was used instead of diphenylamine in Synthesis Example 1- (6). Obtained.

Compound 22 (1.6 g, pale yellow solid, yield 21%) was obtained using the same method as Synthesis Example 1-6.

MS: m / z 1153 [M] ⁺

¹ H NMR (CDCl ₃ ) δ 8.88 (d, 1H), 8.56 (m, 2H), 8.28 (d, 1H), 7.88 (m, 6H), 7.71 (m, 3H), 7.30 (m, 30H), 6.86 (m, 5H), 1.35 (s, 9H), 1.34 (s, 9H)

Synthetic example  12: Synthesis of Compound 26

9,9-dimethyl-N-phenyl-9H-fluoren-2-amine (9,9-dimethyl-N-phenyl-9H-fluoren-2-amine) was used instead of diphenylamine in Synthesis Example 1- (6). Except for using, Compound 26 (2.7 g, pale yellow solid, yield 36%) was obtained in the same manner as in Synthesis example 1.

MS: m / z 985 [M] ⁺

¹ H NMR (CDCl ₃ ) δ 8.89 (s, 1H), 8.37 (m, 3H), 7.64 (m, 7H), 7.24 (m, 33H), 1.42 (s, 6H), 1.36 (s, 6H)

Synthetic example  13: Synthesis of Compound 54

Except for using 2-bromo-9,9-dimethyl-9H-fluorene (2-bromo-9,9-dimethyl-9H-fluorene) instead of bromobenzene in Synthesis Example 2- (1). Then, Compound 54 (3.3 g, pale yellow solid, yield 37%) was obtained using the same method as in Synthesis Example 2.

MS: m / z 1013 [M] ⁺

¹ H NMR (CDCl ₃ ) δ 8.86 (s, 1H), 8.50 (d, 1H), 8.30 (s, 2H), 7.53 (m, 39H), 1.76 (s, 6H), 1.49 (s, 12H)

Synthetic example  14: Synthesis of Compound 64

Synthetic example  14- (1): Synthesis of Intermediate 14-a

Intermediate 14-a was synthesized according to Scheme 13 below:

<Reaction Scheme 13>

                                                       Intermediate 14-a

500 ml of acetic acid and 120 g (1.39 mol) of 3-methyl-2butanone were added to the reaction vessel, and the temperature was raised to 60 degrees. 150 g (1.39 mol) of phenylhydrazine is slowly added dropwise and refluxed. At the end of the reaction, add 500 ml of water and neutralize with sodium hydroxide. Ethyl acetate was added and the extraction was repeated several times, followed by distillation under reduced pressure. Separation by column chromatography gave intermediate 14-a (156 g, 71% yield).

Synthetic example  14- (2): Synthesis of Intermediate 14-b

Intermediate 14-b was synthesized according to Scheme 14 below:

Scheme 14

중간체 14-b

Intermediate 14-b

100 g (0.628 mol) of intermediate 14-a and 500 ml of acetic acid are placed in a reaction vessel. 118g (1.88mo) of sodium cyanoborohydride is slowly added dropwise without excessive heat. After stirring for 5 hours, add 300 ml of water and make basic with sodium hydroxide. The mixture is extracted with ethyl acetate and concentrated several times. Separation by column chromatography gave intermediate 14-b (55 g, yield 54%).

Synthetic example  14- (3): Synthesis of Compound 64

Compound 64 (1.8 g, pale yellow solid, 34% yield) using the same method as Synthesis Example 1, except that Intermediate 14-b was used instead of diphenylamine in Synthesis Example 1- (6). Obtained.

MS: m / z 737 [M] ⁺

¹ H NMR (CDCl ₃ ) δ 8.90 (s, 1H), 8.76 (d, 1H), 8.57 (s, 1H), 8.43 (d, 1H), 7.78 (m, 3H), 7.16 (m, 21H), 4.01 (s, 1H), 3.83 (s, 1H), 1.37 (s, 3H), 1.35 (s, 3H), 1.26 (m, 6H), 1.14 (m, 6H)

Synthesis Example 15 Synthesis of Compound 68

Synthetic example  15- (1): Synthesis of Intermediate 15-a

Intermediate 15-a was synthesized according to Scheme 15 below:

Scheme 15

                                Intermediate 15-a

In a 500 ml round bottom flask, 50 g (0.462 mol) of phenylhydrazine and 170 ml of acetic acid were heated to 60 degrees. To the heated flask was added dropwise 51.9 g (0.462 mol) of 2-methylcyclohexanone. When the drop is completed, reflux for 8 hours. After the reaction was completed, 100 ml of water was added and basified with sodium hydroxide.

The mixture was extracted with water and ethyl acetate, the organic layer was anhydrous with magnesium sulfate, concentrated under reduced pressure, and separated by column chromatography using hexane and ethyl acetate as a developing solvent, to obtain intermediate 15-a (72 g, yield 84%). It was.

Synthetic example  15- (2): Synthesis of Intermediate 15-b

Intermediate 15-b was synthesized according to Scheme 16 below:

Scheme 16

                                      Intermediate 15-b

57 g (0.308 mol) of Intermediate 15-a obtained in Scheme 1 was dissolved in 570 ml of toluene in a 2L round bottom flask with nitrogen atmosphere, and then the temperature was lowered to minus 10 degrees. 300 ml (0.474 mol) of 1.6 M methyllithium were slowly added dropwise to the solution, followed by reaction at minus 10 degrees for 3 hours. After the reaction was completed, water was added slowly until the reaction became inactive.

Extracted with water and ethyl acetate, the organic layer was anhydrous treated with magnesium sulfate and concentrated under reduced pressure. Hexane and ethyl acetate are separated by column chromatography using a developing solvent. Intermediate 15-b (47 g yield 76%) was obtained.

Synthetic example  15- (3): Synthesis of Intermediate 15-c

Intermediate 15-b was synthesized according to Scheme 17 below:

Scheme 17

                                     Intermediate 15-c

In a 1 L round bottom flask, Intermediate 15-b 40g (0.199mol) obtained from Scheme 2, 48.6g (0.238mol) iodobenzene, tris (dibenzylideneacetone) dipalladium (0) 0.89g (0.004mol), 2, 2.47 g (0.004 mol) of 2-bis diphenylphosphino-1,1'-binafryl, 38.19 g (0.397 mol) of sodium tert-butoxide and 400 ml of toluene were added and refluxed for 8 hours. After the reaction was completed, the mixture was laid with celite, filtered, and concentrated under reduced pressure, and separated by column chromatography using hexane as a developing solvent to obtain an intermediate 15-c (44 g, yield 79%).

Synthetic example  15- (4): Synthesis of Intermediate 15-d

Intermediate 15-d was synthesized according to Scheme 18 below:

Scheme 18

                                     Intermediate 15-d

In a 500 ml round bottom flask, 44 g (0.158 mol) of Intermediate 1-c obtained from Scheme 3 and 130 ml of dimethylformamide were added and the temperature was lowered to 0 degrees. 25.2 g (0.142 mol) of N-bromosinimide was dissolved in 220 ml of dimethylformamide and slowly added dropwise. After completion of the dropwise addition, the temperature was raised to room temperature, followed by stirring for 2 hours.

After the reaction was completed, the mixture was extracted with water and dichloromethane and the organic layer was anhydrous with magnesium sulfate and concentrated under reduced pressure. Pour hexane to filter the resulting crystals. Intermediate 15-d (45 g yield 80%) was obtained.

Synthetic example  15- (5): Synthesis of Intermediate 15-e

Intermediate 15-e was synthesized according to Scheme 19 below:

Scheme 19

                                              Intermediate 15-e

In a 1 L round bottom flask, Intermediate 1-d 40 g (0.112 mol) obtained from Scheme 4, 34 g (0.134 mol) bis (pinacolato) diboron, palladium (II) chloride-1-, 1'-bis (diphenylforce) 2.73 g (0.003 mol) of pinot) ferrocene, 32.9 g (0.335 mol) of potassium acetate and 480 ml of toluene were added and refluxed for 8 hours. After the reaction was completed, the mixture was laid with celite, filtered and concentrated under reduced pressure. Hexane and ethyl acetate were separated by column chromatography using a developing solvent to give intermediate 1-e (26 g yield 58%).

Synthetic example  15- (6): Synthesis of Compound 68

In a round bottom flask, Intermediate 1-e 5.0 g (9 mmol), Intermediate 1-e 8.4 g (2.1 mmol), Tetrakistriphenylphosphinepalladium 0.4 g (0.3 mmol), Potassium carbonate 3.6 g (26 mmol), 1,4 -25 ml dioxane, 25 ml toluene and 10 ml water were added and refluxed. When the reaction is completed, add water and hexane. The resulting crystals are filtered off. The crystals were recrystallized to give compound 68 (5.3 g yield 57%).

MS: m / z 969 [M] ⁺

¹ H NMR (CDCl ₃ ) δ 9.07 (d, 1H), 8.95 (m, 2H), 8.48 (d, 1H), 7.75 (m, 6H), 7.37 (m, 24H), 6.62 (s, 2H), 2.00 (m, 2H), 1.60 (m, 14H), 1.30 (s, 3H), 1.28 (s, 3H), 1.18 (s, 3H), 1.15 (s, 3H)

Example  One

The light emitting area of the ITO glass was patterned to have a size of 2 mm × mm and then washed. After mounting the ITO glass in a vacuum chamber, the base pressure was 1 × 10 ⁻⁷ torr, and CuPc was deposited on the ITO to form a hole injection layer having a thickness of 800 Å, and α-NPD on the hole injection layer. Was deposited to form a hole transport layer having a thickness of 300 kHz. Compound BH1 and Compound 1 (3% by weight) were co-deposited on the hole transport layer to form a light emitting layer having a thickness of 250 Pa. Then, Alq ₃ was deposited on the light emitting layer to form an electron transporting layer having a thickness of 350 Pa. Subsequently, a LiF electron injection layer having a thickness of 5 mW and an Al electrode having a thickness of 500 mW were formed in order to complete the organic light emitting device.

Example  2 to 8

An organic light-emitting device was manufactured in the same manner as in Example 1, except that Compound 3, 9, 10, 11, 12, 28, and 29 were used instead of Compound 1.

Comparative example  One

An organic light-emitting device was manufactured in the same manner as in Example 1, except that Compound A was used instead of Compound 1.

<Compound A>

Comparative example  2

An organic light-emitting device was manufactured in the same manner as in Example 1, except that Compound B was used instead of Compound 1.

<Compound B>

Evaluation example  One

For the organic light emitting devices manufactured according to Examples 1 to 8 and Comparative Examples 1 and 2, the driving voltage, current, luminance (measured at 0.4 mA), color coordinates, and lifetime (T80) were measured using the PR650 Spectroscan Source Measurement Unit. Product) and the results are shown in Table 1 below. In addition, the life data is shown in Figures 2 and 3, the current density data is shown in Figures 4 and 5, respectively. T80 means the time taken for the measured luminance to decrease by 80% compared to the initial luminance, measured at 3,000 nit.

Dopant Voltage
(V) Current density
(mA / cm ² ) External quantum
efficiency Whee
(cd / m ² ) CIEx CIEy T80
(hr) Example 1 One 4.0 10 5.61 471 0.145 0.096 187 Example 2 3 3.6 10 6.83 690 0.142 0.123 379 Example 3 9 3.8 10 6.09 695 0.141 0.148 257 Example 4 10 3.8 10 6.33 624 0.143 0.120 207 Example 5 11 4.0 10 6.71 677 0.142 0.125 180 Example 6 12 3.8 10 6.16 693 0.141 0.145 211 Example 7 28 3.8 10 5.43 480 0.145 0.103 150 Example 8 29 3.9 10 6.46 663 0.141 0.127 194 Comparative Example 1 A 4.3 10 5.06 534 0.133 0.137 45 Comparative Example 2 B 4.3 10 4.59 504 0.134 0.144 35

Tables 1 and 2 to 5, it can be seen that the organic light emitting device of Examples 1 to 8 has excellent driving voltage, external quantum efficiency, brightness, color purity and life characteristics compared to the organic light emitting device of Comparative Examples 1 and 2. .

80: second electrode
70: electron injection layer
60: electron transport layer
50: light emitting layer
40: hole transport layer
30: hole injection layer
20: first electrode
10: substrate

Claims (20)

A condensed cyclic compound represented by Formula 1 below:
&Lt; Formula 1 >

In Formula 1,
R ₁ is represented by-(Ar ₁ ) _a1- (R ₁₁ ) _b1 , R ₂ is represented _by- (Ar ₂ ) _a2- (R ₁₂ ) _b2 , and R ₃ is represented _by- (Ar ₃ ) _a3- (R ₁₃ ) _b3 , and R _{4 is-} (Ar ₄ ) _a4- (R ₁₄ ) _b4 ;
Ar ₁ to Ar ₄ are each independently a substituted or unsubstituted C ₅ -C ₆₀ aromatic linking group, or a substituted or unsubstituted C ₂ -C ₆₀ Heteroaromatic linking groups;
Ar ₅ and Ar ₆ are each independently a substituted or unsubstituted C ₅ -C ₆₀ arylene group, or a substituted or unsubstituted C ₂ -C ₆₀ heteroarylene group;
R ₅ , R ₆ and R ₁₁ to R ₁₄ are each independently of the other, an unshared electron pair, hydrogen, deuterium, a substituted or unsubstituted C ₁ -C ₆₀ alkyl group, a substituted or unsubstituted C ₂ -C ₆₀ alkenyl group, a substituted or Unsubstituted C ₂ -C ₆₀ alkynyl group, substituted or unsubstituted C ₁ -C ₆₀ alkoxy group, substituted or unsubstituted C ₃ -C ₆₀ cycloalkyl group, substituted or unsubstituted C ₅ -C ₆₀ aryl group, A substituted or unsubstituted C ₅ -C ₆₀ aryloxy group, a substituted or unsubstituted C ₅ -C ₆₀ arylthio group, a substituted or unsubstituted C ₂ -C ₆₀ heteroaryl group, or a substituted or unsubstituted C _2- A C ₆₀ condensed cyclic group;
A1 to a4 are each independently an integer of 0 to 3;
B1 to b4 are each independently an integer of 1 to 5;
c and d are, independently from each other, an integer from 0 to 3;
X ₁ to X ₁₀ are each independently hydrogen, deuterium, halogen atom, hydroxyl group, cyano group, nitro group, amino group, amidino group, hydrazine, hydrazone, carboxyl group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid or Salts thereof, substituted or unsubstituted C ₁ -C ₆₀ alkyl groups, substituted or unsubstituted C ₂ -C ₆₀ alkenyl groups, substituted or unsubstituted C ₂ -C ₆₀ alkynyl groups, substituted or unsubstituted C ₁ -C ₆₀ alkoxy group, substituted or unsubstituted C ₃ -C ₆₀ cycloalkyl group, substituted or unsubstituted C ₅ -C ₆₀ aryl group, substituted or unsubstituted C ₅ -C ₆₀ aryloxy group, substituted or unsubstituted C _{A 5} -C ₆₀ arylthio group, a substituted or unsubstituted C ₂ -C ₆₀ heteroaryl group, -Si (R ₂₁ ) (R ₂₂ ) (R ₂₃ ) or -N (R ₂₄ ) (R ₂₅ );
R ₂₁ to R ₂₅ are each independently hydrogen, deuterium, substituted or unsubstituted C ₁ -C ₆₀ alkyl group, a substituted or unsubstituted C ₂ -C ₆₀ alkenyl group, a substituted or unsubstituted C ₂ -C ₆₀ alkynyl Nyl group, substituted or unsubstituted C ₁ -C ₆₀ alkoxy group, substituted or unsubstituted C ₃ -C ₆₀ cycloalkyl group, substituted or unsubstituted C ₅ -C ₆₀ aryl group, substituted or unsubstituted C ₅ -C ₆₀ aryloxy group, substituted or unsubstituted C ₅ -C ₆₀ arylthio group, or substituted or unsubstituted C ₂ -C ₆₀ heteroaryl group. The method of claim 1,
R ₁₁ to R ₁₄ are each independently hydrogen, deuterium, a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted pentalenyl group, a substituted or unsubstituted Indenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted azulenyl, substituted or unsubstituted heptalenyl, substituted or unsubstituted indaneyl, Substituted or unsubstituted acenaphthyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted phenalenyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted Unsubstituted anthryl, substituted or unsubstituted fluoranthenyl, substituted or unsubstituted triphenylenyl, substituted or unsubstituted pyrenyl, substituted or unsubstituted Unsubstituted chrysenyl, substituted Or an unsubstituted naphthacenyl group, a substituted or unsubstituted picenyl group, a substituted or unsubstituted perylenyl group, a substituted or unsubstituted pentaxenyl group, a substituted or unsubstituted group Substituted hexacenyl, substituted or unsubstituted cyclopentyl group, substituted or unsubstituted cyclohexyl group, substituted or unsubstituted cycloheptyl group, substituted or unsubstituted dihydronaphthyl group, substituted or unsubstituted A condensed cyclic compound which is a substituted tetrahydronaphthyl group or a substituted or unsubstituted dihydro-indenyl group. The method of claim 1,
Ar ₁ to Ar ₄ are each independently a substituted or unsubstituted benzene linkage, a substituted or unsubstituted pentalene linkage, a substituted or unsubstituted indene linkage, a substituted or unsubstituted naphthalene linkage, a substituted or unsubstituted azulene Linking group, substituted or unsubstituted heptalene linking group, substituted or unsubstituted indacene linking group, substituted or unsubstituted acenaphthalene linking group, substituted or unsubstituted fluorene linking group, substituted or unsubstituted phenylene linking group, substituted or unsubstituted Substituted phenanthrene linkages, substituted or unsubstituted anthracene linkages, substituted or unsubstituted fluoranthene linkages, substituted or unsubstituted triphenylene linkages, substituted or unsubstituted pyrene linkages, substituted or unsubstituted chrysenes Linking group, substituted or unsubstituted naphthacene linking group, substituted or unsubstituted pysene linking group, substituted or unsubstituted perylene linking group, substituted or A condensed cyclic compound which is an unsubstituted pentacene linking group or a substituted or unsubstituted hexacene linking group. The method of claim 1,
a1 to a4 are each independently 0, 1 or 2, and b1 to b4 are each independently 1 or 2, a condensed cyclic compound. The method of claim 1,
R ₁₁ to R ₁₄ are each independently hydrogen, deuterium, or a C ₁ -C ₁₀ alkyl group; Phenyl group; Naphthyl group; Phenanthrenyl group; Fluorenyl group; Pyrenyl group; Cyclopentyl group; Cyclohexyl group; Tetrahydronaphthyl group; Dihydro-indenyl group; And deuterium, halogen atom, hydroxyl group, cyano group, nitro group, amino group, amidino group, hydrazine, hydrazone, carboxyl group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid or salt thereof, C ₁ -C ₆₀ alkyl group, C Phenyl group, naphthyl group, phenanthre substituted with one or more of ₂ -C ₆₀ alkenyl group, C ₂ -C ₆₀ alkynyl group, C ₁ -C ₆₀ alkoxy group, -Si (Q ₁ ) (Q ₂ ) (Q ₃ ) A silyl group, a fluorenyl group, a pyrenyl group, a cyclopentyl group, a cyclohexyl group, a tetrahydronaphthyl group and a dihydro-indenyl group; One of;
Q ₁ to Q ₃ are each independently a C ₁ -C ₁₀ alkyl group or a C ₅ -C ₁₄ aryl group;
Ar ₁ to Ar ₄ are each independently represented by one of the following Chemical Formulas 3A to 3G, a condensed cyclic compound:

In Formulas 3A to 3G
Z ₁₁ to Z ₁₄ are each independently hydrogen, deuterium, halogen atom, hydroxyl group, cyano group, nitro group, amino group, amidino group, hydrazine, hydrazone, carboxyl group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid or Salts thereof, C ₁ -C ₆₀ alkyl groups, C ₂ -C ₆₀ alkenyl groups, C ₂ -C ₆₀ alkynyl groups or C ₁ -C ₆₀ alkoxy groups;
s is an integer from 1 to 6;
t is an integer of 1-3. The method of claim 1, wherein
R ₅ and R ₆ are each independently hydrogen, deuterium, a substituted or unsubstituted C ₁ -C ₁₀ alkyl group, or a substituted or unsubstituted C ₅ -C ₂₀ aryl group, a condensed cyclic compound. The method of claim 1,
R ₅ and R ₆ are each independently hydrogen, deuterium, C ₁ -C ₁₀ alkyl group; Phenyl group; Naphthyl group; And deuterium, halogen atom, hydroxyl group, cyano group, nitro group, amino group, amidino group, hydrazine, hydrazone, carboxyl group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid or salt thereof, C ₁ -C ₆₀ alkyl group, C Phenyl and naphthyl groups substituted with one or more of ₂ -C ₆₀ alkenyl groups, C ₂ -C ₆₀ alkynyl groups and C ₁ -C ₆₀ alkoxy groups; Condensed cyclic compound. The method of claim 1,
Wherein R ₅ and R ₆ are connected to each other with a single bond, a linking group represented by Formula 4A, or a linking group represented by Formula 4B below:
<Formula 4A><Formula4B>

In Formulas 4A and 4B,
X21 to X23 are each independently hydrogen, deuterium, halogen atom, hydroxyl group, cyano group, nitro group, amino group, amidino group, hydrazine, hydrazone, carboxyl group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid or salt thereof , Substituted or unsubstituted C ₁ -C ₆₀ alkyl group, substituted or unsubstituted C ₂ -C ₆₀ alkenyl group, substituted or unsubstituted C ₂ -C ₆₀ alkynyl group, substituted or unsubstituted C ₁ -C ₆₀ alkoxy Groups, substituted or unsubstituted C ₃ -C ₆₀ cycloalkyl groups, substituted or unsubstituted C ₅ -C ₆₀ aryl groups, substituted or unsubstituted C ₅ -C ₆₀ aryloxy groups, substituted or unsubstituted C _5- C ₆₀ arylthio group or a substituted or unsubstituted C ₂ -C ₆₀ heteroaryl group. The method of claim 8,
A condensed cyclic compound represented by any one of Formulas 1A to 1D.
&Lt;

<Formula 1B>

<Formula 1C>

<Formula 1D>

In Formulas 1A to 1D,
The definitions for R ₁ to R ₄ , Ar ₅ , Ar ₆ , c, d and X ₁ to X ₁₀ are as defined in claim 1;
The definitions for X ₂₁ to X ₂₃ are as defined in claim 8;
Z ₂₁ and Z ₂₂ are each independently hydrogen, deuterium, halogen atom, hydroxyl group, cyano group, nitro group, amino group, amidino group, hydrazine, hydrazone, carboxyl group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid Salts thereof, C ₁ -C ₆₀ alkyl groups, C ₂ -C ₆₀ alkenyl groups, C ₂ -C ₆₀ alkynyl groups or C ₁ -C ₆₀ alkoxy groups;
u is an integer from 1 to 4;
v is an integer of 1-6. The method of claim 1,
Condensed cyclic compound in which one or more combinations of R ₁ and R ₂ and R ₃ and R ₄ are connected to each other. The method of claim 10,
In Formula 1, at least one of -N (R ₁ ) (R ₂ ) and -N (R ₃ ) (R ₄ ) is represented by one of the formulas 5A to 5F, condensed cyclic compound:

In Formulas 5A to 5F,
Z ₃₁ to Z ₄₂ are each independently hydrogen, deuterium, halogen atom, hydroxyl group, cyano group, nitro group, amino group, amidino group, hydrazine, hydrazone, carboxyl group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid or Salts thereof, C ₁ -C ₆₀ alkyl groups, C ₂ -C ₆₀ alkenyl groups, C ₂ -C ₆₀ alkynyl groups, C ₁ -C ₆₀ alkoxy groups or C ₅ -C ₆₀ aryl groups;
w and x are, independently from each other, an integer from 1 to 8. The method of claim 1,
A condensed cyclic compound which is the following compound 1, 3, 9, 10, 11, 12, 14, 17, 22, 26, 28, 29, 54, 64 or 68.
<Compound 1><Compound3>

<Compound 9><Compound10>

<Compound 11><Compound12>

<Compound 14><Compound17>

<Compound 22><Compound26>

<Compound 28><Compound29>

<Compound 54><Compound64>

Compound 68

A first electrode; A second electrode opposed to the first electrode; And an organic layer interposed between the first electrode and the second electrode, wherein the organic layer comprises the condensed cyclic compound of any one of claims 1 to 12 in the form of a single material or a combination of different materials. Organic light emitting device. The method of claim 13,
And the organic layer comprises at least one of a functional layer having a hole injection layer, a hole transport layer, a hole injection function, and a hole transport function, a light emitting layer, an electron transport layer, and an electron injection layer. 15. The method of claim 14,
The organic light-emitting device in which the organic layer includes a light emitting layer and the condensed cyclic compound is contained in the light emitting layer. 16. The method of claim 15,
The light emitting layer further comprises a host, wherein the condensed cyclic compound contained in the light emitting layer serves as a dopant. The method of claim 16,
An organic light emitting device, wherein the host is an anthracene-based compound represented by Formula 60:
<Formula 60>

In Formula 60,
Ar ₁₁ and Ar ₁₂ are each independently a substituted or unsubstituted C ₅ -C ₆₀ arylene group;
Ar ₁₃ and Ar ₁₄ are each independently a substituted or unsubstituted C ₁ -C ₁₀ alkyl group or a substituted or unsubstituted C ₅ -C ₆₀ aryl group;
e and f are each independently an integer from 0 to 5. 15. The method of claim 14,
Wherein said organic layer comprises an electron transport layer, and said electron transport layer comprises an electron transport organic compound and a metal-containing material. 19. The method of claim 18,
An organic light emitting device, wherein the metal-containing material is a lithium complex. 15. The method of claim 14,
The organic layer includes at least one of a hole injection layer, a hole transport layer, a hole injection function, and a hole transport function at the same time, at least one of the hole injection layer, the hole transport layer or the hole injection function and a hole transport function At least one of the functional layers comprises a charge-generating material.

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