KR100648050B1 - Organic light emitting device - Google Patents

Abstract

The present invention provides an organic light-emitting device comprising a compound represented by the following formula (1), a compound of formula (1), or a compound in which a thermosetting or photocurable functional group is introduced into the compound.

Organic light emitting device, organic material layer, hole injection material, hole transport material, acridine

Description

Organic light emitting element {ORGANIC LIGHT EMITTING DEVICE}

FIG. 1 shows an example of an organic light emitting element composed of a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4. As shown in FIG.

2 shows an example of an organic light emitting device consisting of a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light emitting layer 7, an electron injection layer 8 and a cathode 4. It is shown.

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

The organic light emitting phenomenon is an example of converting an electric current into visible light by an internal process of a specific organic molecule. The principle of the organic light emitting phenomenon is as follows. When the organic material layer is placed between the anode and the cathode, when a voltage is applied between the two electrodes, electrons and holes are injected into the organic material layer from the cathode and the anode, respectively. Electrons and holes injected into the organic material layer recombine to form excitons, and the excitons fall back to the ground to shine. An organic light emitting device using this principle may generally be composed of an organic material layer including an organic material layer, such as a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer, positioned between the cathode and the anode and the anode and the cathode.

The materials used in the organic light emitting device are mostly pure organic materials or complex compounds in which the organic materials and the metal complexes. The material used in the organic light emitting device may be classified into a hole injection material, a hole transport material, a light emitting material, an electron transport material, an electron injection material and the like according to the use. Here, as the hole injection material or the hole transport material, an organic material having a p-type property, that is, an organic material which is easily oxidized and has an electrochemically stable state during oxidation, is mainly used. On the other hand, as an electron injection material or an electron transport material, organic materials having n-type properties, that is, organic materials that are easily reduced and have an electrochemically stable state at the time of reduction are mainly used. As the light emitting layer material, a material having a p-type property and an n-type property at the same time, that is, a material having a stable form in both oxidation and reduction states, and a material having high luminous efficiency that converts it to light when excitons are formed desirable.

In addition to the above, it is preferable that the material used in the organic light emitting device additionally have the following properties.

First, the material used in the organic light emitting device is preferably excellent in thermal stability. This is because joule heating occurs due to the movement of charges in the organic light emitting diode. Currently, NPB, which is mainly used as a material for the hole transport layer of an organic light emitting device, has a glass transition temperature of less than 100 ° C., and therefore, it is difficult to use in an organic light emitting device requiring a high current.

Second, in order to obtain a high efficiency organic light emitting device that can be driven at a low voltage, holes or electrons injected into the organic light emitting device must be smoothly transferred to the light emitting layer, and the injected holes and electrons must not escape the light emitting layer. For this purpose, the material used for the organic light emitting device should have an appropriate band gap and HOMO or LUMO energy level. PEDOT: PSS, which is currently used as a hole transport material in organic light emitting devices manufactured by the solution coating method, has a low LUMO energy level compared to the LUMO energy level of the organic material used as the light emitting layer material, resulting in high efficiency and long life. There is a difficulty.

In addition, the material used in the organic light emitting device should be excellent in chemical stability, charge mobility, interfacial characteristics with the electrode or the adjacent layer. That is, the material used in the organic light emitting device should be less deformation of the material by moisture or oxygen. In addition, by having an appropriate hole or electron mobility it should be able to maximize the exciton formation by balancing the density of holes and electrons in the light emitting layer of the organic light emitting device. In addition, for the stability of the device should be able to improve the interface with the electrode containing a metal or metal oxide.

There is a need in the art for the development of organic materials having the above requirements.

The present inventors can satisfy the conditions required for materials usable in the organic light emitting device, such as appropriate energy level, electrochemical stability and thermal stability, and a chemical structure that can play various roles required in the organic light emitting device depending on the substituent. It was found that the organic compound having a.

Accordingly, an object of the present invention is to provide an organic compound disclosed by the inventors and an organic light emitting device using the organic compound.

The present invention sequentially stacks a novel compound represented by the following Chemical Formula 1, a compound having a thermosetting or photocurable functional group introduced therein, and an organic material layer including one or more layers including a first electrode, a light emitting layer, and a second electrode. In an organic light-emitting device comprising in the form of, wherein at least one layer of the organic layer comprises a compound of formula (1), or a compound having a thermosetting or photocurable functional group introduced into the compound of formula (1) Provides:

[Formula 1]

In Chemical Formula 1,

X is C or Si,

Ar 1 to Ar 6 are each independently or simultaneously halogen, alkyl, alkenyl, alkynyl, alkoxy, substituted or unsubstituted arylamine group,, substituted or unsubstituted aryl group, substituted or unsubstituted arylalkyl group, Substituted or unsubstituted arylalkenyl group, substituted or unsubstituted heterocyclic group, nitrile group, nitro group and aryl group unsubstituted or substituted with one or more substituents selected from the group consisting of acetylene group, alkyl group, alkenyl group , Alkynyl group, alkoxy group, substituted or unsubstituted arylamine group, aryl group, substituted or unsubstituted arylalkyl group, substituted or unsubstituted arylalkenyl group, substituted or unsubstituted heterocyclic group, nitrile group, nitro group And a heterocyclic group which is unsubstituted or substituted with one or more substituents selected from the group consisting of acetylene groups and which comprises O, N or S as a hetero atom. Can form condensed rings with adjacent groups,

R1 to R10 each independently or simultaneously represent a hydrogen atom alkyl group alkoxy group thioalkoxy group acetylene group; Halogen group, alkyl group, alkenyl group alkoxy group, substituted or unsubstituted arylamine group, substituted or unsubstituted aryl group, substituted or unsubstituted arylalkyl group, substituted or unsubstituted arylalkenyl group, substituted or unsubstituted hetero Alkenyl group substituted or unsubstituted with one or more substituents selected from the group consisting of a cyclic group, a nitrile group and an acetylene group Halogen group, alkyl group, alkenyl group Alkoxy group, substituted or unsubstituted arylamine group, substituted or unsubstituted aryl group , A substituted or unsubstituted arylalkyl group, a substituted or unsubstituted arylalkenyl group, a substituted or unsubstituted alkynyl group halogen group unsubstituted or substituted with one or more substituents selected from the group consisting of a nitrile group and an acetylene group , Alkyl group, alkenyl group alkoxy group, substituted or unsubstituted arylamine group, substituted or unsubstituted aryl group, substituted or unsubstituted arylalkyl group, An aryl group which is unsubstituted or substituted with one or more substituents selected from the group consisting of a ring or an unsubstituted aryl alkenyl group, a substituted or unsubstituted hetero ring group, a nitrile group and an acetylene group, an alkyl group, an alkenyl group alkoxy group, and a substitution Or an unsubstituted arylamine group, a substituted or unsubstituted aryl group, a substituted or unsubstituted arylalkyl group, a substituted or unsubstituted arylalkenyl group, a substituted or unsubstituted heterocyclic group, a nitrile group and an acetylene group Substituted or unsubstituted arylamine group halogen group, alkyl group, alkenyl group alkoxy group, substituted or unsubstituted arylamine group, substituted or unsubstituted aryl group, substituted or unsubstituted arylalkyl group, substituted with one or more substituents selected Or one or more selected from the group consisting of an unsubstituted aryl alkenyl group, a substituted or unsubstituted hetero ring group, a nitrile group and an acetylene group A heterocyclic alkyl group which is unsubstituted or substituted with a vent and contains O, N or S as a hetero atom, an alkenyl group substituted or unsubstituted aryl group, a substituted or unsubstituted arylalkyl group, a substituted or unsubstituted arylalkenyl group Selected from the group consisting of an amino group nitrile group nitro group halogen group amide group and ester group substituted with one or more substituents selected from the group,

Wherein they can form a condensed ring of aliphatic or hetero with groups adjacent to each other,

R3 and R4 and R7 and R8 may be each independently or simultaneously directly connected, or may form a condensed ring together with a group selected from the group consisting of O, S, NR, PR, CRR ', and SiRR'. R and R 'are each independently or simultaneously hydrogen, oxygen, substituted or unsubstituted alkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted alkenyl group, substituted or unsubstituted aryl group, substituted or unsubstituted An arylamine group, a substituted or unsubstituted hetero ring group, an amino group, a nitrile group, a nitro group, a halogen group, an amide group and an ester group,

R11 and R12 are each independently or simultaneously an alkyl group alkoxy group halogen group, alkyl group, alkenyl group, alkynyl group, alkoxy group, substituted or unsubstituted arylamine group, substituted or unsubstituted aryl group, substituted or unsubstituted arylalkyl group , A substituted or unsubstituted aryl alkenyl group, a substituted or unsubstituted heterocyclic group, a nitrile group and an aryl group substituted or unsubstituted with one or more substituents selected from the group consisting of an acetylene group, an alkyl group, an alkenyl group alkoxy group, A group consisting of a substituted or unsubstituted arylamine group, a substituted or unsubstituted aryl group, a substituted or unsubstituted arylalkyl group, a substituted or unsubstituted arylalkenyl group, a substituted or unsubstituted heterocyclic group, a nitrile group and an acetylene group Heterocyclic group nitrile group amide group which is unsubstituted or substituted with one or more substituents selected from and includes O, N or S as a hetero atom. It is selected from the group consisting of a hotel.

Wherein the substituent which may be substituted in the alkyl group, alkenyl group, alkoxy group, aryl group or hetero ring is halogen, alkyl group, alkenyl group alkoxy group, arylamine group, aryl group, arylalkyl group, aryl alkenyl group, heterocyclic group, Nitrile group or acetylene group.

When explaining the substituent of Formula 1 in detail.

Specific examples of Ar 1 to Ar 6 in Formula 1 include, but are not limited to, groups of the following formula.

In the above formula, Y and Y 'are each selected from the group consisting of hydrogen, a halogen group, an alkyl group, an alkenyl group alkoxy group, an arylamine group, an aryl group, a heterocyclic group, a nitrile group and an acetylene group, which are connected to each other and condensed May form a ring.

Examples of the halogen group include fluorine, chlorine, bromine or iodine, and examples of the arylamine group include diphenyl amine group, petyl naphthyl amine group, ditolyl amine group, phenyl tolyl amine group, carbazole group, and triphenyl. And amine groups. Examples of the aryl groups include phenyl, naphthyl, anthranyl, and biphenyl groups. Examples of heterocyclic groups include pyridyl groups, acridil groups, thiophene groups, imidazole groups, oxazole groups, Thiazole groups or quinolinyls, although not limited thereto.

It is preferable that the alkyl group, the alkoxy group, and the alkenyl group in R1-R12 of the said Formula (1) are C1-C20.

Examples of the aryl group in R1 to R12 of Formula 1 are as follows, but are not limited thereto.

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

Examples of the arylamine group in R1 to R12 of Chemical Formula 1 are as follows, but are not limited thereto.

,

,

,

,

Examples of the heterocyclic group in R1 to R12 of Formula 1 are as follows, but are not limited thereto.

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

N of the thiophene in the substituent is 1 to 6 and R is an alkyl or a substituted or unsubstituted aryl group.

Examples of the arylalkenyl group in R1 to R12 of Chemical Formula 1 are as follows, but are not limited thereto.

Examples of the halogen group in R1 to R12 of Formula 1 include fluorine, chlorine, bromine or iodine.

In the above formula, Z is a group consisting of hydrogen, C1-C20 alkyl group, C1-C20 alkenyl group, C1-C20 alkynyl group, alkoxy group, arylamine group, aryl group, heterocyclic group, nitrile group and acetylene group Is the group selected from Specific examples of the arylamine group, aryl group, and heterocyclic group in Z include the examples described in the substituents of R1 to R12 described above.

Preferred compounds of the present invention X in formula 1 is C or Si, R3 and R4 is hydrogen, R3 and R4 is directly connected or selected from the group consisting of O, S, NR, PR, CRR ', and SiRR' And a compound to form a condensed ring together with the group (wherein R and R ′ are as defined in Formula 1).

In another preferred compound of the present invention, X in Formula 1 is C or Si, and R3 and R4 and R7 and R8 are each independently or simultaneously directly connected or O, S, NR, PR, CRR ', and SiRR'. A compound which forms a condensed ring together with a group selected from the group consisting of (wherein R and R 'are as defined in Formula 1).

In the exemplary embodiment of the present invention, CRR ′ may be a ketone group (C (═O)).

Another preferred compound of the invention is a compound of formula

 [Formula 2]

In the above formula,

Ar1 to Ar6, R11 and R12 are as defined in the formula (1).

Another preferred compound of the invention is a compound of formula

[Formula 3]

In the above formula,

Ar1 to Ar6, R11 and R12 are as defined in the formula (1).

Specific examples of the compound of Formula 1 include compounds represented by the following formula. However, the compounds of the following formulas are intended to aid the understanding of the present invention, and are not intended to limit the scope of the present invention.

[Formula 1-1] [Formula 1-2]

[Formula 1-3] [Formula 1-4]

[Formula 1-5] [Formula 1-6]

[Formula 1-7] [Formula 1-8]

[Formula 1-9] [Formula 1-10]

[Formula 1-11] [Formula 1-12]

[Formula 1-13] [Formula 1-14]

[Formula 1-15] [Formula 1-16]

[Formula 1-17] [Formula 1-18]

 [Formula 1-19] [Formula 1-20]

[Formula 1-21] [Formula 1-22]

[Formula 1-23] [Formula 1-24]

[Formula 1-25] [Formula 1-26]

[Formula 1-27]

[Formula 1-28]

In the core structure of the compound of Formula 1, diarylamine and phenyl substituted with diarylamine are substituted on the basic skeleton of acridine. Various substituents are introduced into the basic structure to have suitable properties for use as an organic material layer of the organic light emitting device. Specifically, it is as follows.

The core structure of the compound represented by Chemical Formula 1 has a structure in which a aryl substituted with an arylamine at a paraaryl position and a diarylamine at a basic skeleton of acridine is substituted. In this structure, since the carbon atoms or silicon atoms forming X have sp ³ bonds, the plane forming the acridine skeleton and the plane including R11 and R12 have a three-dimensional structure perpendicular to each other. Conjugation will not occur. Due to such structural properties, the core structure of the compound of Formula 1 has limited conjugation.

The conjugation length of the compound and the energy bandgap are closely related. Specifically, the longer the conjugation length of the compound, the smaller the energy bandgap. As described above, the core structure of the compound of Chemical Formula 1 has a large energy band gap since the conjugation structure is limited.

In the present invention, a compound having various energy band gaps can be synthesized by introducing various substituents into the R1 to R12 and Ar1 to Ar6 positions of the core structure having a large energy band gap as described above. In general, it is easy to control the energy band gap by introducing a substituent into the core structure having a large energy band gap, but when the core structure has a small energy band gap, it is difficult to largely control the energy band gap by introducing a substituent. In addition, in the present invention, the HOMO and LUMO energy levels of the compound may be controlled by introducing various substituents into R1 to R12 and Ar1 to Ar6 of the core structure as described above.

Moreover, the compound which has the intrinsic property of the introduced substituent can be synthesize | combined by introducing various substituents into the core structure of the above structure. For example, by introducing a substituent mainly used in the hole injection layer material, the hole transport layer material, the light emitting layer material, the electron transport layer material used in the manufacture of the organic light emitting device to the core structure it can synthesize a material that meets the requirements required for each organic material layer have. In particular, since the compound of Formula 1 includes an aryl amine structure in the core structure, the compound of Formula 1 may have an appropriate energy level as a hole injection and / or hole transport material in the organic light emitting device. In the present invention, a device having a low driving voltage and high light efficiency may be realized by selecting a compound having an appropriate energy level among the compounds of Formula 1 and using the compound in an organic light emitting device.

For example, in relation to the energy band gap and the energy level, the compound of Chemical Formula 1-18 has an energy level suitable for use as a hole injection layer or a hole transport layer because the HOMO is 5.24 eV. On the other hand, the bandgap of the compound of Formula 1-18 is still 3.3 eV, which is very large compared to the bandgap of NPB which is usually used as a hole transport layer material, the LUMO value of this material is also very high as about 1.94 eV. When a compound having a high LUMO value is used as the hole transport layer, this increases the energy wall with LUMO of the material used as the light emitting layer, thereby preventing electrons from entering the hole transport layer from the light emitting layer. Therefore, such a compound can improve the luminous efficiency of the organic light emitting device compared to conventional NPB (HOMO 5.4 eV, LUMO 2.3 eV, energy band gap 3.1 eV) and the like. In the present invention, the energy bandgap was calculated using the general method of calculating by the UV-VIS spectrum.

In addition, the compound of Formula 1 exhibits stable redox characteristics. Redox stability can be confirmed using CV (cyclovoltammetry) method. As a specific example, it was shown that the compound of Formula 1-18 was oxidized at the same voltage and showed the same amount of current when multiple repeated oxidation voltages were applied, indicating that the compound had excellent stability against oxidation. Indicates.

On the other hand, the compound of Formula 1 has a high glass transition temperature (Tg) is excellent in thermal stability. For example, it can be seen that the compound of Formula 1-18 has a glass transition temperature of 120 ° C., which is significantly higher than that of NPB (Tg: 96 ° C.). The excellent thermal stability of such compounds is an important factor in providing drive stability to the device.

In addition, the compound of Formula 1 may be formed of an organic material layer by a solution coating method as well as a vacuum deposition method in the manufacture of the organic light emitting device. Here, the solution coating method means spin coating, dip coating, inkjet printing, screen printing, spray method, roll coating and the like, but is not limited thereto.

For example, the compound of Formula 1-18 is very excellent in solubility in solvents used in the device manufacturing process, for example, polar solvents such as xylene, dichloroethane or NMP, etc., as well as very thin film formation in the method using a solution Because of its good properties, a solution coating method can be used in the manufacture of the device. In addition, it is common to see that the emission wavelength in the thin film or the solid state formed by the solution coating method is shifted to the longer wavelength than the emission wavelength in the solution state due to the intermolecular interaction, and has the same structure as the compound of Chemical Formula 1 In compounds, such shifts in wavelength are very small.

The compound of Formula 1 is a method of reacting a lithiated alkyl or aryl group with a carbonyl group of an ester group to obtain a tertiary alcohol, and then heating the material under an acid catalyst to form a hexagonal cyclic compound as water is released. It can be prepared using. Such a preparation method is a method well known in the art, and those skilled in the art can prepare the compound of Formula 1 by changing the conditions of the preparation method. The specific manufacturing method was illustrated in the manufacture example mentioned later.

In the organic light emitting device of the present invention, a compound having a thermosetting or photocurable functional group introduced into the compound of Formula 1 may be used instead of the compound of Formula 1. Such a compound may be formed of an organic material layer by a method of maintaining the basic physical properties of the compound of Chemical Formula 1 described above and forming a thin film by a solution coating method and then curing the device.

As described above, a method of forming an organic material layer by introducing a curable functional group into an organic material and forming a thin film of the organic material by a solution coating method and then curing the organic light emitting device is described in US Patent Publication No. 2003-0044518 and Europe. Patent Publication 1146574 A2 and the like.

In the above documents, an organic light emitting device having a multilayer structure by a solution coating method in the case of forming an organic light emitting device by forming the organic material layer by the above method using a material having a thermosetting or photocurable vinyl group or an acryl group It is described that not only can be made but also an organic light emitting device of low voltage and high brightness. This principle of action can also be applied to the compounds of the present invention.

In the present invention, the thermosetting or photo-curable functional group may be a vinyl group or an acrylic group.

The organic light emitting device of the present invention may be manufactured by materials and methods known in the art, except that at least one layer of the organic material layer includes the compound of the present invention, that is, the compound of Formula 1.

The organic material layer of the organic light emitting device of the present invention may have a single layer structure, but may have a multilayer structure in which two or more organic material layers are stacked. For example, the organic light emitting device of the present invention may have a structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer and the like as an organic material layer. However, the structure of the organic light emitting device is not limited thereto and may include a smaller number of organic material layers.

In addition, the organic light emitting device of the present invention may be manufactured by sequentially stacking a first electrode, an organic material layer, and a second electrode on a substrate, for example. In this case, a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation may be used, but is not limited thereto.

The preparation method of the compound of Formula 1 and the preparation of the organic light emitting device using the same will be described in detail in the following Preparation Examples and Examples. However, the following Preparation Examples and Examples are intended to illustrate the present invention, and the scope of the present invention is not limited thereto.

Preparation Example 1

Synthesis of Compound 1-18

Synthesis of Compound A

16.9 g of diphenyl amine, 16.7 mL of 2-iodo methyl benzoate, 15.2 g of potassium carbonate, 7.0 g of copper powder, and 15.6 g of sodium sulfate were added to 50 mL of nitrobenzene, and stirred at a temperature of 190 to 200 ° C for one day. The mixture was cooled to room temperature, dissolved in THF, and filtered. After the filtrate was removed to remove the solvent, ethanol was added to the resulting mixture and stirred. The solid obtained by filtration was dissolved in THF, passed through silica gel, and then the solvent was removed, stirred in acetone to crystallize, and the obtained solid was filtered to give 22.4 g of product.

Synthesis of Compound B

18.2 g of Compound A was dissolved in 150 mL of purified THF, cooled to 0 ° C., and slowly added thereto a 1.6 M solution of methyl lithium dispersed in ethyl ether. The reaction was slowly warmed to room temperature, stirred for one day, and then quenched with water. The reaction was then extracted with ethyl ether and the residual moisture was removed from the organic layer and then the organic solvent was removed. To the resulting yellow liquid, n-hexane was added and stirred while boiling, and then cooled to room temperature and filtered. The solid obtained by filtration was washed with n-hexane and dried in vacuo to give 11.86 g of the product.

To 11.86 g of the material obtained above, 100 mL of acetic acid and 0.5 mL of concentrated hydrochloric acid were added, followed by stirring for 40 minutes. The reaction was cooled to room temperature, acetic acid was removed under reduced pressure, and ethanol was added thereto and stirred. The resulting solid was filtered to yield 9.5 g of a white product.

NMR (CDCl ₃ ): 7.67-7.63 (t, 2H), 7.55-7.51 (t, 1H), 7.49-7.47 (d, 2H), 7.38-7.35 (d, 2H), 7.01-6.92 (t, t, 4H), 6.30-6.28 (d, 2H), 1.72 (s, 6H)

MS: [M + H] ⁺ = 286

HOMO: 5.80 eV

Band Gap: 3.7 eV

LUMO: 2.10 eV

Synthesis of Compound C

8.56 g of compound B was dissolved in 300 mL of chloroform, and 4.67 mL of bromine was slowly added thereto. The reaction was stirred for 2 hours, water and a small amount of acetone were added to terminate the reaction, and the water layer and the organic layer were separated. Water was removed from the organic layer, passed through silica gel using chloroform, and then the organic solvent was removed and solidified by adding ethanol to obtain 12.28 g of a white solid.

NMR (CDCl ₃ ): 7.79-7.75 (d, 2H), 7.52-7.50 (s, 2H), 7.20 -7.15 (d, 2H), 7.09-7.04 (d, 2H), 6.14-6.10 (d, 2H) , 1.63 (s, 6H)

Synthesis of Compound 1-18

1.044 g of the compound C and 1.117 g of diphenylamine were dissolved in 10 mL of xylene, and 0.769 g of sodium-t-butoxide, 0.110 g of tris (dibenzylideneacetone) dipaldium (0), tri-tert-butyl 0.036 g of phosphine was added sequentially and then stirred while boiling for 4 hours. After the reaction was cooled to room temperature, the reaction was terminated with water and extracted with xylene. Water was removed from the organic layer using magnesium sulfate anhydride, and then the organic solvent was removed, and the resulting liquid was column separated with tetrahydrofuran / n-hexane = 1/19 to obtain 1.26 g of the product.

MS: [M + H] ⁺ = 787

HOMO: 5.24

Band gap = 3.3 eV

LUMO: 1.94 eV

Tg: 120 ℃

Preparation Example 2

Synthesis of Compound 1-14

Synthesis of Intermediate A in Preparation Example 1 was carried out in the same manner, except that diphenyl amine was substituted with carbazole.

Preparation Example 3

Synthesis of Compound 1-21

Synthesis of Intermediate B in Preparation Example 1 was conducted in the same manner except for using phenyl lithium instead of methyl lithium.

Preparation Example 4

Synthesis of Compound 1-23

Synthesis of Intermediate A in Preparation Example 1 was carried out in the same manner, except that diphenyl amine was synthesized by substituting with carbazole and phenyl-1-naphthyl amine was used instead of diphenyl amine in the final compound.

Preparation Example 5

Synthesis of Compound 1-24

Synthesis of the final compound in Preparation Example 1 was carried out in the same manner except for using carbazole instead of diphenylamine.

Preparation Example 6

Synthesis of Compound 1-26

Synthesis of the final compound in Preparation Example 4 was prepared in the same manner, except for using carbazole instead of phenyl-1-naphthyl amine.

Preparation Example 7

Synthesis of Compound 1-20

Synthesis of Intermediate A in Preparation Example 4 was carried out in the same manner, except for using phenothiazine instead of carbazole.

 [Production of Organic Light-Emitting Element]

Example 1

A glass substrate (corning 7059 glass) coated with a thin film of ITO (indium tin oxide) at a thickness of 1000 ?? was placed in distilled water in which detergent was dissolved and ultrasonically washed. At this time, Fischer Co. was used as a detergent and Millipore Co. was used as distilled water. Secondly filtered distilled water was used as a filter of the product. After washing ITO for 30 minutes, ultrasonic washing was performed twice with distilled water for 10 minutes. After distilled water washing, ultrasonic cleaning with a solvent of isopropyl alcohol, acetone, methanol, dried, and then transferred to a plasma cleaner. The substrate was dry cleaned for 5 minutes at 85 W at 14 mtorr pressure using nitrogen plasma and then transferred to a vacuum evaporator.

Hexonitrile hexaazatriphenylene (hereinafter referred to as HAT), a compound of the following formula, was thermally vacuum deposited to a thickness of 500 kPa on an ITO transparent electrode prepared as described above, and an anode having an ITO conductive layer and an n-type organic material. Was formed.

[HAT]

Compound 1400 (400 kPa) was vacuum deposited on the layer to form a hole injection and transport layer. Alq3 was vacuum deposited to a thickness of 300 kPa on the hole transport layer to form a light emitting layer. The electron transport layer material of the following formula was deposited on the light emitting layer to a thickness of 200 Å to form an electron transport layer.

[Electron transport material]

12 전자 thick lithium fluoride (LiF) and 2000 Å thick aluminum were sequentially deposited on the electron transport layer to form a cathode.

In the above process, the deposition rate of the organic material was maintained at 0.3 ~ 0.8 Å / sec. In addition, the lithium fluoride of the negative electrode maintained a deposition rate of 0.3 kPa / sec and aluminum of 1.5 to 2.5 kPa / sec. During deposition, the degree of vacuum was maintained at 1 to 3 × 10 ⁻⁷ .

The fabricated device showed an electric field of 8.14 V at a forward current density of 100 mA / cm ² and showed green light emission with a light efficiency of 0.53 lm / W.

As described above, when the device operates at the driving voltage and emits light, the compound of Formula 1-18, which forms a layer between the hole injection layer and the light emitting layer, plays a role of hole transport.

Example 2

HAT was deposited to a thickness of 80 kHz on the ITO substrate prepared in the same manner as in Example 1 to form an anode having an ITO conductive layer and an n-type organic material. Subsequently, the compound of Formula 1-18 was deposited to a thickness of 800 kPa on the anode to form a hole injection layer.

NPB was deposited on the hole injection layer to a thickness of 300 kW to form a hole transport layer, and then Alq3 was deposited to a thickness of 300 kW to form a light emitting layer. An electron transport layer and a cathode were formed on the light emitting layer in the same manner as in Example 1.

In this embodiment, the deposition rate of the organic material and the cathode and the vacuum during deposition were maintained the same as in Example 1.

The fabricated device showed an electric field of 9.94 V at a forward current density of 100 mA / cm ² and showed green light emission with a light efficiency of 1.44 lm / W.

As described above, when the device operates at the driving voltage and emits light, the compound of Formula 1-18, which forms a layer between the thin film formed on the substrate and the hole transport layer, functions as a hole injection.

The compound of the present invention can be used as an organic layer material, especially a hole injection material and / or a hole transport material in the organic light emitting device, when the compound is used in the organic light emitting device to lower the driving voltage of the device, improve the light efficiency, the compound Thermal stability of the device can improve the life characteristics of the device.

Claims (9)

Compound represented by the following formula (1) [Formula 1]

In Chemical Formula 1, X is C or Si, Ar 1 to Ar 6 are each independently or simultaneously halogen, alkyl, alkenyl, alkynyl, alkoxy, substituted or unsubstituted arylamine group, substituted or unsubstituted aryl group, substituted or unsubstituted arylalkyl group, substituted or Unsubstituted arylalkenyl group, substituted or unsubstituted heterocyclic group, nitrile group, nitro group and aryl group unsubstituted or substituted with one or more substituents selected from the group consisting of acetylene group, alkyl group, alkenyl group, alky Nyl group, alkoxy group, substituted or unsubstituted arylamine group, aryl group, substituted or unsubstituted arylalkyl group, substituted or unsubstituted arylalkenyl group, substituted or unsubstituted heterocyclic group, nitrile group, nitro group and acetylene Heterocyclic group which is unsubstituted or substituted with one or more substituents selected from the group consisting of groups and includes O, N or S as a heteroatom, wherein To form condensed rings with adjacent groups, R1 to R10 are each independently or simultaneously an alkyl group having 1 to 20 hydrogen atoms, alkoxy group having 1 to 20 carbon atoms, thioalkoxy group, acetylene group, halogen group, alkyl group, alkenyl group, alkynyl group, alkoxy group, thioalkoxy group, substituted or unsubstituted A group consisting of a substituted arylamine group, a substituted or unsubstituted aryl group, a substituted or unsubstituted arylalkyl group, a substituted or unsubstituted arylalkenyl group, a substituted or unsubstituted heterocyclic group, a nitrile group, a nitro group and an acetylene group Alkenyl group substituted or unsubstituted with one or more substituents selected from halogen, alkyl, alkenyl, alkynyl, alkoxy, thioalkoxy, substituted or unsubstituted arylamine group, substituted or unsubstituted aryl group, substituted Or an unsubstituted arylalkyl group, a substituted or unsubstituted arylalkenyl group, a substituted or unsubstituted heterocyclic group, a nitrile group, a nitro group and an acetylene group Aryl group unsubstituted or substituted with one or more substituents selected from the group halogen group, alkyl group, alkenyl group, alkynyl group, alkoxy group, thioalkoxy group, substituted or unsubstituted arylamine group, substituted or unsubstituted aryl group, substituted Or an arylamine group unsubstituted or substituted with one or more substituents selected from the group consisting of an unsubstituted arylalkyl group, a substituted or unsubstituted arylalkenyl group, a substituted or unsubstituted heterocyclic group, a nitrile group, a nitro group, and an acetylene group. Halogen group, alkyl group, alkenyl group, alkynyl group, alkoxy group, thioalkoxy group, substituted or unsubstituted arylamine group, substituted or unsubstituted aryl group, substituted or unsubstituted arylalkyl group, substituted or unsubstituted arylalke Hetero-substituted or unsubstituted with one or more substituents selected from the group consisting of a silyl group, a substituted or unsubstituted hetero ring group, a nitrile group, a nitro group, and an acetylene group At least one substituent selected from the group consisting of O, N or S heterocyclic alkyl group, alkenyl group substituted or unsubstituted aryl group, substituted or unsubstituted arylalkyl group, substituted or unsubstituted arylalkenyl group Substituted amino group nitrile group nitro group halogen group amide group imide group and ester group Wherein they can form a condensed ring of aliphatic or hetero with groups adjacent to each other, R3 and R4 and R7 and R8 may be each independently or simultaneously directly connected, or may form a condensed ring together with a group selected from the group consisting of O, S, NR, PR, CRR ', and SiRR'. R and R 'are each independently or simultaneously hydrogen, oxygen, substituted or unsubstituted alkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted alkenyl group, substituted or unsubstituted aryl group, substituted or unsubstituted An aryl amine group, a substituted or unsubstituted hetero ring group, an amino group, a nitrile group, a nitro group, a halogen group, an amide group, an imide group, and an ester group, R11 and R12 each independently or simultaneously represent an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, a thioalkoxy group, a substituted or unsubstituted arylamine group, and a substitution. Or one or more substituents selected from the group consisting of an unsubstituted aryl group, a substituted or unsubstituted arylalkyl group, a substituted or unsubstituted arylalkenyl group, a substituted or unsubstituted heterocyclic group, a nitrile group, a nitro group and an acetylene group. Substituted or unsubstituted aryl group halogen group, alkyl group, alkenyl group alkoxy group, substituted or unsubstituted arylamine group, substituted or unsubstituted aryl group, substituted or unsubstituted arylalkyl group, substituted or unsubstituted arylalke Substituted or unsubstituted and substituted with one or more substituents selected from the group consisting of a silyl group, a substituted or unsubstituted hetero ring group, a nitrile group, a nitro group, and an acetylene group Heterocyclic group nitrile group nitro group amide group imide group and ester group containing O, N, or S are included. The compound of claim 1, wherein Ar 1 to Ar 6 in Formula 1 are each independently or simultaneously selected from the group consisting of groups represented by the following Formulas:

In the above formula, Y and Y 'are each selected from the group consisting of hydrogen, halogen group, alkyl group, alkenyl group, alkynyl group, alkoxy group, arylamine group, aryl group, heterocyclic group, nitrile group and acetylene group, which are Can be connected to each other to form a condensed ring. According to claim 1, wherein in Formula 1 X is C or Si, R3 and R4 and / or R7 and R8 are each independently or simultaneously directly connected or form a condensed ring together with a group selected from the group consisting of O, S, NR, PR, CRR ', and SiRR', wherein R and R 'are as defined in Formula 1). The compound of claim 1, wherein the compound of Formula 1 is represented by the following Formula 2 or [Formula 2]

[Formula 3]

In Chemical Formulas 2 and 3, Ar1 to Ar6, R11 and R12 are as defined in the formula (1). The compound of claim 1, wherein a thermosetting or photocurable functional group is introduced into the compound of formula 1. An organic light emitting device comprising a first electrode, an organic material layer including one or more layers including a light emitting layer, and a second electrode in a stacked form, wherein one or more layers of the organic material layers are any one of claims 1 to 5. An organic light-emitting device comprising a compound of one term. The organic light emitting device of claim 6, wherein the organic material layer comprises a hole transport layer, and the hole transport layer comprises the compound of any one of claims 1 to 5. The organic light emitting device of claim 6, wherein the organic material layer includes a hole injection layer, and the hole injection layer comprises the compound of any one of claims 1 to 5. The organic light emitting device of claim 6, wherein the organic material layer includes a layer for simultaneously injecting holes and transporting holes, and the layer includes the compound of any one of claims 1 to 5.

Images