KR20180127112A - Compound for forming capping layer and organic electroluminescent divice including the same - Google Patents

Abstract

The present invention relates to a compound for forming a capping layer and an organic light emitting device including the same. The compound for forming a capping layer according to the present invention is applied to the organic light emitting device to improve external light emitting efficiency, color coordinates, and lifetime of the organic light emitting device. The compound is represented by a following formula 1.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a compound for forming a capping layer and an organic light-

The present invention relates to a compound for forming a capping layer and an organic light emitting device including the same.

Generally, an organic light emitting element refers to a device that converts electric energy into light energy using an organic material. The organic light emitting diode may have a structure in which an anode is formed on a substrate, and a hole transport layer, a light emitting layer, an electron transport layer, and a cathode are sequentially formed on the anode.

When a voltage is applied between the anode and the cathode, holes are injected from the anode, and the injected holes are transferred to the light emitting layer via the hole transporting layer. At the same time, electrons are injected from the cathode, To the light emitting layer. The holes and electrons transferred to the light emitting layer are recombined to generate excitons. The excitons are changed from an excited state to a ground state and light is generated.

The efficiency of an organic light emitting device can be generally divided into an internal light emitting efficiency and an external light emitting efficiency. The internal luminous efficiency is related to how efficiently the excitons are generated in the organic layer formed between the first electrode and the second electrode, such as the hole transport layer, the light emitting layer, and the electron transport layer, and photo-conversion is performed. Theoretically, the internal luminous efficiency is known to be about 25% for fluorescence and about 100% for phosphorescence.

On the other hand, the external luminous efficiency represents the efficiency with which the light generated in the organic layer formed between the first and second electrodes is extracted to the outside of the organic light emitting device, and is generally extracted to the outside at a level of about 20% have.

Various organic compounds have been applied as a capping layer in order to prevent external light from being totally lost due to the external light emitting efficiency, ie, a method for increasing light extraction. In order to improve the performance of the organic light emitting device, Efforts have been made to develop organic compounds having high refractive index and thin film stability capable of improving external light emitting efficiency.

Korean Patent Publication No. 10-2004-0098238

The present invention relates to a compound for forming a capping layer which has a wide band gap that does not affect the RGB wavelength of the organic light emitting device and has a high refractive index to improve the color purity of the organic light emitting device and the external light emitting efficiency, The present invention provides an organic light emitting device having a capping layer containing a compound for forming a light emitting layer.

However, the problems to be solved by the present invention are not limited to the problems described above, and other problems not described can be clearly understood by those skilled in the art from the following description.

The first aspect of the present invention provides a compound for forming a capping layer, which is represented by the following Formula 1 and is interposed between one side of an electrode of an organic light emitting device:

[Chemical Formula 1]

In Formula 1,

Ar is a heteroaryl group of the substituted or unsubstituted C _{6 ~ 50} aryl group, or a substituted or unsubstituted C _{5 ~ 50} of the ring,

Ar _1, and Ar ₂ are each independently a substituted or unsubstituted aryl group of C _6-50, or a substituted or unsubstituted heteroaryl of _{5 ~} C ₅₀ group,

The Ar, Ar ₁ , and Ar ₂ Lt; / RTI > is substituted or unsubstituted spirofluor fluorene,

R ₁ to R ₃ are each independently hydrogen, deuterium, a substituted or unsubstituted C _{1 ~ 30} alkyl group, a substituted or unsubstituted C _{1 ~ 30} alkoxy group, a substituted or unsubstituted C _{2 ~ 30} ring ring of the alkenyl group , a substituted or unsubstituted aryl group of C _6-50, or a substituted or unsubstituted heteroaryl of _{5 ~} C ₅₀ group,

1 is an integer of 0 to 4, and m is an integer of 0 to 3.

The second aspect of the present invention provides a plasma processing apparatus comprising: first and second electrodes; And a capping layer disposed outside at least one of the first and second electrodes and containing a compound for forming a capping layer according to the present invention.

The capping layer forming compound according to an embodiment of the present invention has a wide band gap that does not affect the RGB wavelength of the organic light emitting device and has a high refractive index to improve the color purity of the organic light emitting device and the external light emitting efficiency have.

In addition, the capping layer forming compound according to an embodiment of the present invention is excellent in the thin film arrangement of molecules and forms a stable thin film as the packing density is increased, and the thin film is formed from heat generated when driving the organic light emitting device with high Tg and Td And the contamination of the inside of the organic light emitting element from external moisture can be reduced, so that the lifetime of the organic light emitting element can be improved.

1 is a schematic view of an organic light emitting device according to an embodiment of the present invention.

Hereinafter, embodiments and examples of the present invention will be described in detail with reference to the accompanying drawings, which will be readily apparent to those skilled in the art to which the present invention pertains.

It should be understood, however, that the present invention may be embodied in many different forms and is not limited to the embodiments and examples described herein. In order to clearly illustrate the present invention, parts not related to the description are omitted, and similar parts are denoted by like reference characters throughout the specification.

Throughout this specification, when a member is "on " another member, it includes not only when the member is in contact with the other member, but also when there is another member between the two members.

Throughout this specification, when an element is referred to as "including " an element, it is understood that the element may include other elements as well, without departing from the other elements unless specifically stated otherwise. The terms "about "," substantially ", etc. used to the extent that they are used throughout the specification are intended to be taken to mean the approximation of the manufacturing and material tolerances inherent in the stated sense, Accurate or absolute numbers are used to help prevent unauthorized exploitation by unauthorized intruders of the referenced disclosure. The word " step (or step) "or" step "used to the extent that it is used throughout the specification does not mean" step for.

Throughout this specification, the term "combination thereof" included in the expression of the machine form means one or more combinations or combinations selected from the group consisting of the constituents described in the expression of the machine form, And the like.

Throughout this specification, the description of "A and / or B" means "A or B, or A and B".

Throughout the specification, the term "aryl" refers to a C _5-35 aromatic hydrocarbon ring group such as phenyl, benzyl, naphthyl, biphenyl, terphenyl, fluorene, phenanthrenyl, Means an aromatic ring such as phenyl, naphthyl, neopentyl, neopentyl, neopentyl, neopentyl, neopentyl, neopentyl, neopentyl, neopentyl, neopentyl, neopentyl, Examples of the C _3-35 aromatic ring containing a hetero element include pyrrolyl, pyrazinyl, pyridinyl, indolyl, isoindolyl, furyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, Benzothiophenyl, dibenzothiophenyl, quinolyl, isoquinolyl, quinoxalinyl, carbazolyl, phenanthridinyl, acridinyl, phenanthrolinyl, thienyl, and pyridine rings, pyrazine rings, pyrimidine rings , Pyridazine ring, triazine ring, indole ring, quinoline ring , Acridine rings, pyrrolidine rings, dioxane rings, piperidine rings, morpholine rings, piperazine rings, carbazole rings, furan rings, thiophene rings, oxazole rings, oxadiazole rings, May include a heterocyclic group formed from a heterocyclic ring, a thiazole ring, a thiadiazole ring, a thiadiazole ring, a benzothiazole ring, a triazole ring, an imidazole ring, a benzimidazole ring, a pyran ring or a dibenzofuran ring .

"Optionally substituted" term throughout the present specification is a deuterium, a halogen, an amino group, a nitrile group, a nitro group or a C ₁ ~ C ₃₀ alkyl group, C ₂ ~ C ₃₀ alkenyl group, C ₁ ~ C ₃₀ of the alkoxy group, Means a group selected from the group consisting of a C ₃ to C ₂₀ cycloalkyl group, a C ₃ to C ₂₀ heterocycloalkyl group, a C ₆ to C ₃₀ aryl group, and a C ₃ to C ₃₀ heteroaryl group can do. In addition, throughout the present specification, the same symbols may have the same meanings unless otherwise specified.

The first aspect of the present invention provides a compound for forming a capping layer, which is represented by the following Formula 1 and is interposed between one side of an electrode of an organic light emitting device:

[Chemical Formula 1]

In Formula 1,

Ar is a heteroaryl group of the substituted or unsubstituted C _{6 ~ 50} aryl group, or a substituted or unsubstituted C _{5 ~ 50} of the ring,

Ar ₁ And Ar ₂ are each independently a substituted or unsubstituted aryl group of C _6-50, substituted or unsubstituted heteroaryl of _{5 ~} C ₅₀ group,

The Ar, Ar _{1 ,} and Ar ₂ Lt; / RTI > is substituted or unsubstituted spirofluor fluorene,

R ₁ to R ₃ are each independently hydrogen, deuterium, a substituted or unsubstituted C _{1 ~ 30} alkyl group, a substituted or unsubstituted C _{1 ~ 30} alkoxy group, a substituted or unsubstituted C _{2 ~ 30} ring ring of the alkenyl group , a substituted or unsubstituted aryl group of C _6-50, or a substituted or unsubstituted heteroaryl of _{5 ~} C ₅₀ group,

1 is an integer of 0 to 4, and m is an integer of 0 to 3.

The compound for forming a capping layer of Formula 1 according to an embodiment of the present invention has a structure in which a carbazole is linked to an arylamine through an arylene linking group.

The compound according to the present invention has a high refractive index by having an arylene linking group between the carbazole and the arylamine, and the intermolecular packing is excellent in the production of the thin film, so that a stable capping layer can be formed. Thus, the external light emitting efficiency, color coordinate, and lifetime of the organic light emitting device can be improved.

If the capping layer containing the compound according to one embodiment of the present invention is disposed outside the electrode of the organic light emitting device, the external light emitting efficiency can be improved. When the light generated in the organic layer interposed between the first and second electrodes of the organic light emitting diode is extracted to the outside of the organic light emitting diode, the light emitted to the outside can be prevented from being totally lost and lost.

The compound for forming a capping layer according to an embodiment of the present invention may have a high refractive index due to its structural characteristics and is excellent in thin film stability. When applied as a capping layer of an organic light emitting device, the external light emitting efficiency, The life can be improved.

In one embodiment of the present invention, Ar may be substituted or unsubstituted phenylene, naphthylene, biphenylene, terphenylene, fluorenyl, or combinations thereof.

Further, in one embodiment of the present invention, Ar ₁ and Ar ₂ may each independently be phenyl, naphthyl, biphenyl, terphenyl, fluorene, or a combination thereof.

Also, in one embodiment of the present invention, R < ₁ > may be phenyl or biphenyl.

In one embodiment of the present invention, the compound for forming the capping layer may be represented by the following general formula (2) or (3).

[Chemical Formula 2] < EMI ID =

In Formula 2 or Formula 3,

R ₄ to R ₇ are each independently hydrogen, deuterium, a substituted or unsubstituted C _{1 ~ 25} alkyl group, a substituted or unsubstituted C _{1 ~ 25} alkoxy group, a substituted or unsubstituted C _{2 ~ 25} ring of the alkenyl group , a substituted or unsubstituted aryl group of C _6-25, or a substituted or unsubstituted heteroaryl of _{5 ~} C ₂₅ group,

n, o, p, and q are each independently an integer of 0 to 4,

L, L ₁ and L ₂ are each independently a direct bond, a substituted or unsubstituted C _6-15 aryl group, or a substituted or unsubstituted C _5-25 heteroarylene group.

In the compound represented by Formula 2, the arylamine has a spirobifluorene substituent, and the compound represented by Formula 3 is carbazole and arylamine are connected through spirobifluorene.

The compounds represented by Chemical Formulas 2 and 3 may include spirobifluorene to increase the refractive index and the external quantum efficiency, and thus are very suitable for the capping layer. In addition, a wide band gap that can not absorb the wavelength of the RGB region of the organic light emitting element is maintained, so that the color purity of the organic light emitting element may not be lowered.

In addition, the compounds represented by Chemical Formulas 2 and 3 are excellent in molecular arrangement and intermolecular packing to form a stable thin film, and the lifetime can be improved by protecting the organic light emitting element from external air and moisture.

In addition, the compounds represented by Chemical Formulas 2 and 3 can inhibit intermolecular recrystallization with high Tg and Td, and can be stable from heat generated during driving.

Further, in one embodiment of the present invention, the compound for forming the capping layer may be represented by the following formula (4) or (5).

[Chemical Formula 4]

The compound represented by Formula 4 has an arylamine having spirobifluorene, and nitrogen is connected to the position 2 of spirobifluorene.

In addition, the compound represented by the general formula (5) has carbazole and arylamine connected through positions 2 and 7 of spirobifluorene. Compounds having such a structure can maintain a linear shape in a molecular structure, so that the arrangement of the thin film molecules is excellent and the stability is excellent, so that the external light emitting efficiency and lifetime of the organic light emitting device can be maximized.

Further, in one embodiment of the present invention, the compound for forming the capping layer may be represented by the following formula (6) or (7).

[Chemical Formula 6] < EMI ID =

The compound represented by the formula (6) is connected to the arylamine through the 3-position of the carbazole, the arylamine has the spirobifluorene, and the nitrogen of the arylamine is connected to the position 2 of the spirobifluorene.

In addition, the compound represented by the general formula (7) is connected to the arylamine through the 3-position of the carbazole, and the carbazole and the arylamine are connected through the positions 2 and 7 of the spirobifluorene. Compounds having such a structure can further maintain the linearity in the molecular structure, and the thin film-like molecular arrangement is excellent, and the stability is excellent, so that the external light emitting efficiency and lifetime of the organic light emitting device can be maximized.

 Further, in one embodiment of the present invention, Ar may be substituted or unsubstituted phenylene, naphthylene, biphenylene, terphenylene, fluorenyl, or a combination thereof.

Further, in one embodiment of the present invention, Ar < _{1 >} And Ar ₂ can each independently be phenyl, naphthyl, biphenyl, terphenyl, fluorene, or combinations thereof.

Also, in one embodiment of the present invention, R < ₁ > may be phenyl or biphenyl.

In one embodiment of the present invention, the compounds for forming a capping layer represented by Chemical Formulas 1 to 7 may be synthesized by the following reaction schemes, but not limited thereto, and may be synthesized by various methods.

[Reaction Scheme]

In one embodiment of the present invention, the compound represented by Formula 1 may be any one of compounds 1 to 445 shown below, but not limited thereto:

The second aspect of the present invention provides an organic light emitting device having a capping layer comprising a compound represented by any one of Chemical Formulas 1 to 7 disposed therein.

According to an embodiment of the present invention, an organic light emitting device includes a first electrode and a second electrode; An organic material layer interposed between the first and second electrodes; And a capping layer disposed outside one of the first and second electrodes, the capping layer containing the compound for forming a capping layer according to any one of claims 1 to 7. Here, the side adjacent to the organic material layer interposed between the first electrode and the second electrode on both sides of the first electrode or the second electrode is referred to as the inner side, and the side not adjacent to the organic material layer is referred to as the outer side. That is, when the capping layer is disposed outside the first electrode, the first electrode is interposed between the capping layer and the organic material layer, and when the capping layer is disposed outside the second electrode, the second electrode is interposed between the capping layer and the organic material layer. do.

According to an embodiment of the present invention, the organic light emitting device may include various organic layers on the inner side of the first electrode and the second electrode, and a capping layer may be formed on the outer side of at least one of the first and second electrodes. have. The capping layer may be formed on the outer side of the first electrode and on the outer side of the second electrode, or on the outer side of the first electrode or the outer side of the second electrode. The capping layer may include a compound for forming a capping layer according to the present invention. In addition, according to an embodiment of the present invention, an organic layer having an additional function may be formed on the outer sides of the first and second electrodes with the capping layer interposed therebetween.

According to one embodiment of the present invention, the capping layer may contain the compound for forming the capping layer according to an embodiment of the present invention, or may include two or more compounds or a known compound.

The organic light emitting device according to an embodiment of the present invention includes one or more organic layers between first and second electrodes, that is, inside first and second electrodes, and a capping layer Can be formed. The organic material layer may be a hole transporting layer, a light emitting layer, and an electron transporting layer which generally constitute a light emitting portion, but may not be limited thereto.

The organic light emitting diode includes a hole injecting layer (HIL), a hole transporting layer (HTL), a light emitting layer (EML), an electron transporting layer (ETL), an electron injecting layer Layer (EIL), and the like.

For example, the organic light emitting device can be fabricated as shown in FIG. The organic light emitting device includes a first electrode (anode, hole injecting electrode 1000), a capping layer 3000, a hole injecting layer 200, a hole transporting layer 300, a light emitting layer 400, an electron transporting layer 500, Electron injection layer 600 / second electrode (cathode, electron injection electrode 2000 / capping layer 3000) may be stacked in this order.

As described above, the compound for forming a capping layer according to an embodiment of the present invention has a high refractive index by having an aryl linking group and an arylamine between a carbazole and an arylamine, has excellent intermolecular packing in the production of a thin film, . Thus, the external light emitting efficiency, color coordinate, and lifetime of the organic light emitting device can be improved.

1, the substrate 100 may be a transparent glass substrate or a flexible plastic substrate having excellent mechanical strength, thermal stability, transparency, surface smoothness, ease of handling, and waterproofness. have.

The hole injection electrode 1000 is used as an anode for hole injection of the organic light emitting element. A material having a low work function may be used to inject holes and may be formed of a transparent material such as indium tin oxide (ITO), indium zinc oxide (IZO), or graphene.

A hole injecting layer material may be deposited on the anode electrode by a method such as vacuum deposition, spin coating, casting, or Langmuir-Blodgett (LB) method. When the hole injection layer is formed by the vacuum deposition method, the deposition conditions vary depending on the compound used as the material of the hole injection layer 200, the structure and thermal characteristics of the desired hole injection layer, and the like. deposition temperature, 10 ^- can be properly selected from a deposition rate, layer thickness of 10Å to 5㎛ range of ⁸ to 10 ^-3 torr vacuum, 0.01 to 100Å / sec in the. Further, the charge generating layer can be further deposited on the surface of the hole injecting layer as required. As the charge generation layer material, a usual material can be used, for example, HATCN.

Next, a hole transporting layer material may be deposited on the hole injection layer 200 by a method such as vacuum deposition, spin coating, casting, or LB method to form the hole transporting layer 300. When the hole transporting layer is formed by the vacuum deposition method, the deposition conditions vary depending on the compound used, but it is generally preferable to select the conditions within the substantially same range as the formation of the hole injection layer.

The hole transport layer 300 may be formed using a known compound. According to an embodiment of the present invention, the hole transport layer 300 may be formed of one or more layers, and the light emitting auxiliary layer may be formed on the hole transport layer 300.

The light emitting layer material may be deposited on the hole transport layer 300 or the light emitting auxiliary layer by a method such as vacuum deposition, spin coating, casting, or LB method. When the light emitting layer is formed by the vacuum vapor deposition method, the deposition conditions vary depending on the compound used, but it is generally preferable to select the conditions within the substantially same range as the formation of the hole injection layer. The light emitting layer material may be a known compound as a host or a dopant.

When the phosphorescent dopant is used together with the phosphorescent dopant, a hole blocking material (HBL) may be further deposited by vacuum evaporation or spin coating to prevent triplet excitons or holes from diffusing into the electron transport layer. The hole blocking material that can be used at this time is not particularly limited, but any known hole blocking material may be used. For example, an oxadiazole derivative, a triazole derivative, a phenanthroline derivative, or a hole blocking material described in Japanese Patent Laid-Open Publication No. 11-329734 (A1) can be exemplified. Typically, Balq (bis Phenanthrolines based compounds such as UDC company BCP (bassocouroin), and the like can be used.

An electron transport layer 500 is formed on the light emitting layer 400 formed as described above. The electron transport layer may be formed by vacuum deposition, spin coating, casting, or the like. The deposition conditions of the electron transporting layer depend on the compound used, but it is generally preferable to select the conditions within the same range as the formation of the hole injection layer.

Then, an electron injection layer material may be deposited on the electron transport layer 500 to form an electron injection layer 600. The electron injection layer may be formed by vacuum deposition, spin coating, casting, And the like.

The hole injecting layer 200, the hole transporting layer 300, the light emitting layer 400, and the electron transporting layer 500 of the organic light emitting device may be formed of any of the following materials.

A cathode 2000 for electron injection is formed on the electron injection layer 600 by a vacuum evaporation method or a sputtering method. As the cathode, various metals may be used. Specific examples thereof include aluminum, gold, silver, and magnesium.

The organic light emitting device of the present invention can have an organic light emitting device having various structures as well as an anode, a hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, an electron injecting layer and a cathode structure, Layer or an intermediate layer of two layers may be further formed.

As described above, the thickness of each organic material layer formed according to the present invention can be controlled according to the required degree, specifically 10 to 1,000 nm, and more specifically, 20 to 150 nm.

According to an embodiment of the present invention, a capping layer 3000 may be formed on the outside of the electrode where the hole injection layer 200 is interposed in the anode 1000 electrode. In addition, a capping layer 3000 may be formed outside the electrode where the electron injection layer 600 is interposed in the cathode (3000) electrode. Although not limited thereto, the capping layer 3000 may be formed by a deposition process and may be formed to a thickness of 300 to 900 ANGSTROM.

In the organic light emitting device according to this aspect, all of the contents described in the first aspect of the present application may be applied, but the present invention is not limited thereto.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the scope of the present invention is not limited by these Examples.

[ Example ]

Intermediate synthesis

For the synthesis of the desired compound, the intermediate OP can be synthesized by the following reaction scheme.

Production Example 1 : Intermediate (OP1)

30.0 g of the above 2-bromo-9,9'-spirobi [fluorene], 5.6 g of aniline, 11 g of t-BuONa, 2.8 g of Pd ₂ (dba) ₃ and 3.5 ml of (t- Bu) ₃ P were added to a round- And the mixture was stirred under reflux. After confirming the reaction by TLC, water was added and the reaction was terminated. The organic layer was extracted with MC, filtered under reduced pressure, and recrystallized to obtain 22.6 g of OP1 (yield: 73%).

OP2 to OP10 were synthesized in the same manner as in OP1 by the starting materials as shown in Table 1 below.

Starting material for OP2 Starting material for OP3 Starting material for OP4

,

,

,

,

2-bromo-9,9'-spirobi [fluorene], naphthalen-1-amine 2-bromo-9,9'-spirobi [fluorene], naphthalen-2-amine 2-bromo-9,9'-spirobi [fluorene], [1,1'-biphenyl] -4-amine Starting material for OP5 Starting material of OP6 Starting material for OP7

,

,

,

2-bromo-9,9'-spirobi [fluorene], [1,1'-biphenyl] -3-amine 2-bromo-9,9'-spirobi [fluorene], [1,1'-biphenyl] -2-amine 2-bromo-9,9'-spirobi [fluorene], 4- (naphthalen-1-yl) aniline Starting material of OP8 Starting material of OP9 Starting material for OP10

,

,

,

2-bromo-9,9'-spirobi [fluorene], 4- (naphthalen-2-yl) aniline 2,7-dibromo-9,9'-spirobi [fluorene], N-phenyl- [1,1'-biphenyl] -4-amine 2,7-dibromo-9,9'-spirobi [fluorene], di ([1,1'-biphenyl] -4-yl) amine

Compound synthesis

Using the intermediates OP1 to OP10, the following compounds 1 to 15 were synthesized as follows.

Compound 1 Synthesis

3.0 g of the 3- (4-bromophenyl) -9-phenyl-9H-carbazole, 3.1 g of OP1, 1.1 g of t-BuONa, 0.3 g of Pd ₂ (dba) ₃ and (t-Bu) ₃ PO 4 were added to a round bottom flask. Were dissolved in 100 ml of toluene, and the mixture was stirred under reflux. After confirming the reaction by TLC, water was added and the reaction was terminated. The organic layer was extracted with MC, filtered under reduced pressure, and recrystallized to obtain 3.7 g (yield: 67%) of Compound 1. m / z: 724.29 (100.0%), 725.29 (59.9%), 726.29 (17.8%), 727.30

Synthesis of Compound 2

Compound 2 was synthesized by using OP2 instead of OP1 in the same manner as Compound 1. [ (Yield: 61%) m / z: 774.30 (100.0%), 775.31 (64.2%), 776.31 (20.3%), 777.31

Synthesis of Compound 3

Compound 3 was synthesized by using OP3 instead of OP1 in the same manner as in Compound 1. [ (Yield: 64%) m / z: 774.30 (100.0%), 775.31 (64.2%), 776.31 (20.3%), 777.31

Synthesis of Compound 4

Compound 4 was synthesized by using OP4 in place of OPl in the same manner as Compound 1. [ (Yield: 67%) m / z: 800.32 (100.0%), 801.32 (66.7%), 802.33 (21.7%), 803.33

Synthesis of Compound 5

Compound 5 was synthesized by using OP5 in place of OPl in the same manner as in Compound 1. (Yield: 59%) m / z: 800.32 (100.0%), 801.32 (66.7%), 802.33 (21.7%), 803.33

Synthesis of Compound 6

Compound 6 was synthesized by using OP6 in place of OPl in the same manner as in Compound 1. (Yield: 65%) m / z: 800.32 (100.0%), 801.32 (66.7%), 802.33 (21.7%), 803.33

Synthesis of Compound 7

Compound 7 was synthesized by using OP7 in place of OP1 in the same manner as in Compound 1. (Yield: 60%) m / z: 850.33 (100.0%), 851.34 (70.8%), 852.34 (25.2%), 853.34

Synthesis of Compound 8

Compound 8 was synthesized by using OP8 in place of OPl in the same manner as in Compound 1. (Yield 64%) m / z: 850.33 (100.0%), 851.34 (70.8%), 852.34 (25.2%), 853.34 (5.7%)

Synthesis of Compound 9

([1,1'-biphenyl] -4-yl) -3- (4-bromophenyl) -9H-carbazole instead of 3- (4-bromophenyl) -9- Was used to synthesize Compound 9. (Yield: 62%) m / z: 800.32 (100.0%), 801.32 (66.7%), 802.33 (21.7%), 803.33

Synthesis of Compound 10

Bromo [1,1'-biphenyl] -4-yl) -9-phenyl-9H-carbazole instead of 3- (4-bromophenyl) Compound 10 was synthesized using carbazole. (Yield: 66%) m / z: 800.32 (100.0%), 801.32 (66.7%), 802.33 (21.7%), 803.33

Synthesis of Compound 11

(4'-bromo- [1,1'-biphenyl] -4-yl) -9-phenyl-9-carbazole instead of 3- (4-bromophenyl) Compound 11 was synthesized using 9H-carbazole and OP4. M / z: 876.35 (100.0%), 877.35 (73.2%), 878.36 (26.2%), 879.36 (6.2%), 880.36 (1.1%).

Synthesis of Compound 12

(4'-bromo- [1,1'-biphenyl] -4-yl) -9-phenyl-9-carbazole instead of 3- (4-bromophenyl) Compound 9 was synthesized using 9H-carbazole and OP5. M / z: 876.35 (100.0%), 877.35 (73.2%), 878.36 (26.2%), 879.36 (6.2%), 880.36

Synthesis of Compound 13

(4'-bromo- [1,1'-biphenyl] -4-yl) -9-phenyl-9-carbazole instead of 3- (4-bromophenyl) Compound 9 was synthesized using 9H-carbazole and OP6. M / z: 876.35 (100.0%), 877.35 (73.2%), 878.36 (26.2%), 879.36 (6.2%), 880.36

Synthesis of Compound 14

Compound 14 was synthesized by using 3-bromo-9-phenyl-9H-carbazole and OP9 instead of 3- (4-bromophenyl) -9-phenyl-9H- (Yield: 60%) m / z: 800.32 (100.0%), 801.32 (66.7%), 802.33 (21.7%), 803.33

Synthesis of Compound (15)

Compound 15 was synthesized by using 3-bromo-9-phenyl-9H-carbazole and OP10 instead of 3- (4-bromophenyl) -9-phenyl-9H- M / z: 876.35 (100.0%), 877.35 (73.2%), 878.36 (26.2%), 879.36 (6.2%), 880.36

Organic Light Emitting Device Manufacturing

Example  One

The hole injection layer HI01 was formed to a thickness of 600 Å, HATCN 50 Å, and a hole transport layer was formed to a thickness of 600 Å on an ITO substrate having a reflective layer containing Ag. The light emitting layer was doped with BH01: BDO0 3% to form a 250 Å film. Next, Alq3: Liq (1: 1) 300 Å was deposited as an electron transport layer, and 10 Å of LiF was deposited to form an electron injection layer. Subsequently, MgAg was deposited to a thickness of 15 nm as a cathode, and Compound 1 was deposited as a capping layer on the cathode to a thickness of 600 ANGSTROM. This device was encapsulated in a glove box to produce an organic light emitting device.

Example  2 to Example  15

An organic light emitting device was fabricated in the same manner as in Example 1 except that a capping layer was formed using Compound 2 to Compound 15 instead of Compound 1 in Example 1.

Comparative Example  1 to Comparative Example  6

An organic light emitting device was fabricated in the same manner as in Example 1, except that the compound 1 was replaced with the following compound Ref.1 to Ref.6 to form a capping layer.

[Evaluation of performance of organic light emitting device]

A voltage was applied to the Keithley 2400 source measurement unit to inject electrons and holes and the luminance was measured using a Konica Minolta spectroscope (CS-2000). The performance of the organic light-emitting device of Examples and Comparative Examples was evaluated by measuring the current density and the luminance with respect to the applied voltage under the atmospheric pressure condition, and the results are shown in Table 2, respectively.

Op. V mA / cm2 Cd / A QE (%) CIEy CIEy LT97 Example 1 4.01 10 8.50 7.41 0.139 0.060 120 Example 2 4.00 10 8.48 7.35 0.140 0.060 118 Example 3 4.00 10 8.47 7.33 0.140 0.060 118 Example 4 4.02 10 8.63 7.50 0.139 0.060 124 Example 5 4.00 10 8.55 7.40 0.138 0.060 120 Example 6 4.00 10 8.60 7.46 0.140 0.060 124 Example 7 3.98 10 8.50 7.37 0.140 0.061 120 Example 8 3.99 10 8.52 7.40 0.140 0.061 120 Example 9 4.01 10 8.50 7.38 0.140 0.061 120 Example 10 3.99 10 8.75 7.65 0.140 0.060 132 Example 11 4.00 10 8.73 7.65 0.139 0.060 130 Example 12 4.00 10 8.70 7.67 0.140 0.060 127 Example 13 3.99 10 8.70 7.60 0.139 0.060 130 Example 14 4.00 10 8.42 7.18 0.140 0.060 119 Example 15 4.01 10 8.40 7.19 0.140 0.061 121 Comparative Example 1 4.00 10 7.15 6.00 0.143 0.070 97 Comparative Example 2 4.02 10 7.01 5.95 0.143 0.071 90 Comparative Example 3 4.02 10 6.30 5.34 0.144 0.075 55 Comparative Example 4 4.01 10 6.72 5.60 0.144 0.074 85 Comparative Example 5 4.00 10 6.90 5.85 0.143 0.070 82 Comparative Example 6 4.00 10 6.41 5.43 0.145 0.078 70

As shown in Table 1, it can be seen that the embodiments of the present invention greatly improve the external light emitting efficiency, color purity and lifetime in comparison with Comparative Examples 1 to 6.

More specifically, in comparison with Comparative Example 1 in which nitrogen of the carbazole and spirobifluorene are connected, Comparative Example 2 in which no coupling group is present between carbazole and arylamine, and Comparative Examples 3 to 6 in which spirobifluorene is not contained, Examples 1-15 of the invention have phenyl or biphenyl substituents on the nitrogen of the carbazole and may have a refractive index. Further, in Examples 1 to 15, the carbazole is connected to the arylamine through the arylene linking group to maintain a large bandgap, and can have a high refractive index. Further, in Examples 1 to 15, the molecular arrangement and the intermolecular packing can be improved because the coupling groups of the carbazole and the arylamine or the substituent of the arylamine have the spirobifluorene having the picoconjugation not the alkylfluorene. Further, Examples 1 to 15 have high Tg and Td even at a relatively low molecular weight due to spirobifluorene, so that recrystallization and thermal stability of the thin film can be excellent.

That is, it has been confirmed that when the capping layer is formed on the organic light emitting device using the compound for forming a capping layer according to an embodiment of the present invention, the efficiency, color coordinates and lifetime of the organic light emitting device can be improved.

It will be understood by those of ordinary skill in the art that the foregoing description of the embodiments is for illustrative purposes and that those skilled in the art can easily modify the invention without departing from the spirit or essential characteristics thereof. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive. For example, each component described as a single entity may be distributed and implemented, and components described as being distributed may also be implemented in a combined form.

The scope of the present invention is defined by the appended claims rather than the detailed description, and all changes or modifications derived from the meaning and scope of the claims and their equivalents should be interpreted as being included in the scope of the present invention .

100: substrate
200: Hole injection layer
300: hole transport layer
400: light emitting layer
500: electron transport layer
600: electron injection layer
1000: anode (first electrode)
2000: cathode (second electrode)
3000: capping layer

Claims (9)

A compound for forming a capping layer, which is represented by the following formula (1) and is disposed outside an electrode of an organic light emitting device:
[Chemical Formula 1]

In Formula 1,
Ar is a heteroaryl group of the substituted or unsubstituted C _{6 ~ 50} aryl group, or a substituted or unsubstituted C _{5 ~ 50} of the ring,
Ar ₁ And Ar ₂ are each independently a substituted or unsubstituted aryl group of C _6-50, or a substituted or unsubstituted heteroaryl of _{5 ~} C ₅₀ group,
At least one of Ar, Ar &_lt; ₁ &_gt; and Ar < ₂ > is a substituted or unsubstituted spirobifluorene,
R ₁ to R ₃ are each independently hydrogen, deuterium, a substituted or unsubstituted C _{1 ~ 30} alkyl group, a substituted or unsubstituted C _{1 ~ 30} alkoxy group, a substituted or unsubstituted C _{2 ~ 30} ring ring of the alkenyl group , a substituted or unsubstituted aryl group of C _6-50, or a substituted or unsubstituted heteroaryl of _{5 ~} C ₅₀ group,
1 is an integer of 0 to 4, and m is an integer of 0 to 3. The method according to claim 1,
The compound is a compound for forming a capping layer represented by the following Chemical Formula 2 or 3:
[Chemical Formula 2] < EMI ID =

In Formula 2 or Formula 3,
R ₄ to R ₇ are each independently hydrogen, deuterium, a substituted or unsubstituted C _{1 ~ 25} alkyl group, a substituted or unsubstituted C _{1 ~ 25} alkoxy group, a substituted or unsubstituted C _{2 ~ 25} ring of the alkenyl group , a substituted or unsubstituted aryl group of C _6-25, or a substituted or unsubstituted heteroaryl of _{5 ~} C ₂₅ group,
n, o, p, and q are each independently an integer of 0 to 4,
L, L ₁ and L ₂ are each independently a direct bond, a substituted or unsubstituted aryl group of C _{6 ~ 25} pills, or substituted or unsubstituted heteroaryl group of C _{5 ~ 25.} 3. The method of claim 2,
The compound is a compound for forming a capping layer represented by the following Chemical Formula 4 or 5:
[Chemical Formula 4]

The method of claim 3,
The compound is a compound for forming a capping layer represented by the following Chemical Formula 6 or 7:
[Chemical Formula 6] < EMI ID =

The method according to claim 1,
And Ar is a substituted or unsubstituted phenylene, naphthylene, biphenylene, terphenylene, fluorenyl, or a combination thereof. The method according to claim 1,
The Ar ₁ And Ar ₂ are each independently phenyl, naphthyl, biphenyl, terphenyl, fluorene, or combinations thereof. The method according to claim 1,
Wherein the capping layer forming compound is any one of the following compounds:

First and second electrodes;
An organic material layer interposed between the first and second electrodes; And
And a capping layer disposed outside one of the first and second electrodes and containing a compound for forming a capping layer according to any one of claims 1 to 7. 9. The method of claim 8,
Wherein the capping layer has a thickness of 300 to 900 ANGSTROM.

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