KR101686077B1 - Compound for organic optoelectric device, organic optoelectric device and display device - Google Patents

Abstract

상기 화학식 1에서, A¹, A², X, R¹ 내지 R⁵, L¹ 내지 L³는 명세서 내에 정의된 바와 같다.The present invention relates to a compound for an organic optoelectronic device, an organic optoelectronic device including the same, and a display device including the organic optoelectronic device.
[Chemical Formula 1]

In Formula 1, A ¹ , A ² , X, R ¹ to R ⁵ , and L ¹ to L ³ are as defined in the specification.

Description

Technical Field [0001] The present invention relates to a compound for an organic optoelectronic device, an organic optoelectronic device including the same, and a display device including the organic optoelectronic device. BACKGROUND OF THE INVENTION [0002]

A compound for an organic optoelectronic device, an organic optoelectronic device including the same, and a display device including the organic optoelectronic device.

Organic optoelectronic devices are devices that can switch between electrical and optical energy.

Organic optoelectronic devices can be roughly classified into two types according to the operating principle. One is an optoelectronic device in which an exciton formed by light energy is separated into an electron and a hole, the electron and hole are transferred to different electrodes to generate electric energy, and the other is a voltage / Emitting device that generates light energy from energy.

Examples of organic optoelectronic devices include organic optoelectronic devices, organic light emitting devices, organic solar cells, and organic photo conductor drums.

In recent years, organic light emitting diodes (OLEDs) have attracted considerable attention due to the demand for flat panel display devices. The organic light emitting diode is a device for converting electrical energy into light by applying an electric current to the organic light emitting material, and usually has an organic layer inserted between an anode and a cathode. The organic layer may include a light emitting layer and an optional auxiliary layer. The auxiliary layer may include, for example, a hole injecting layer, a hole transporting layer, an electron blocking layer, an electron transporting layer, And a hole blocking layer.

The performance of the organic light emitting device is greatly influenced by the characteristics of the organic layer, and the organic layer is highly affected by the organic material contained in the organic layer.

In particular, in order for the organic light emitting device to be applied to a large-sized flat panel display device, it is necessary to develop an organic material capable of increasing the mobility of holes and electrons and increasing the electrochemical stability.

And which can provide an organic optoelectronic device having characteristics such as high efficiency, long life, and the like.

An organic optoelectronic device including the compound for an organic optoelectronic device, and a display device including the organic optoelectronic device.

In one embodiment of the present invention, there is provided a compound for an organic optoelectronic device represented by the following formula (1).

[Chemical Formula 1]

In the above formula (1), the definition of each substituent is as described in the following "Detailed Description of the Invention ".

According to another embodiment of the present invention, there is provided an organic electroluminescent device comprising: an anode facing each other; a cathode; and at least one organic layer positioned between the anode and the cathode, Thereby providing an organic optoelectronic device.

In another embodiment of the present invention, there is provided a display device including the above-described organic optoelectronic device.

The organic optoelectronic device including the compound for an organic optoelectronic device according to an embodiment of the present invention has excellent electrochemical and thermal stability, has excellent lifetime characteristics, and can have a high luminous efficiency even at a low driving voltage.

1 and 2 are sectional views showing an organic light emitting device according to an embodiment, respectively.

Hereinafter, embodiments of the present invention will be described in detail. However, it should be understood that the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.

As used herein, unless otherwise defined, at least one of the substituents or at least one hydrogen in the compound is substituted with one or more substituents selected from the group consisting of deuterium, a halogen group, a hydroxy group, an amino group, a substituted or unsubstituted C1 to C30 amine group, a nitro group, C1 to C10 alkyl groups such as a C1 to C40 silyl group, a C1 to C30 alkyl group, a C1 to C10 alkylsilyl group, a C3 to C30 cycloalkyl group, a C6 to C30 aryl group, a C1 to C20 alkoxy group, a fluoro group, A trifluoroalkyl group or a cyano group.

The substituted or unsubstituted C 3 to C 40 silyl group, the C 1 to C 30 alkyl group, the C 1 to C 10 alkylsilyl group, the substituted or unsubstituted C 3 to C 20 amino group, the substituted or unsubstituted C 3 to C 40 silyl group, C30 to C10 cycloalkyl group, a C6 to C30 aryl group, a C1 to C20 alkoxy group, a fluoro group, a trifluoromethyl group, or a C1 to C10 trifluoroalkyl group or a cyano group may be fused to form a ring have. Specifically, the substituted C6 to C30 aryl group may be fused with an adjacent substituted or unsubstituted C3 to C40 silyl group to form a ring.

In this specification, a portion indicated by a dotted line in the chemical structural formula indicates that it can be represented by a single bond or a double bond. Specifically, the moiety represented by the dotted line between A ¹ and A ² in the chemical formula represented by Chemical Formula 1 in the present specification is represented by -Ca ² - when a -A ¹ -C- is a double bond, When CA ² - is a double bond, -A ¹ -C- means that it can be represented as a single bond.

Means one to three heteroatoms selected from the group consisting of N, O, S and P in one functional group, and the remainder is carbon, unless otherwise defined.

As used herein, unless otherwise defined, the term "alkyl group" means an aliphatic hydrocarbon group. The alkyl group may be a "saturated alkyl group" which does not contain any double or triple bonds.

The alkyl group may be an alkyl group having from 1 to 20 carbon atoms. More specifically, the alkyl group may be a C1 to C10 alkyl group or a C1 to C6 alkyl group. For example, C1 to C4 alkyl groups mean that from 1 to 4 carbon atoms are included in the alkyl chain and include methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl, sec- Indicating that they are selected from the group.

Specific examples of the alkyl group include a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, And the like.

The term "aryl group" used herein means a substituent in which all the elements of the cyclic substituent have p-orbital and the p-orbital forms a conjugation, and the monocyclic or fused-ring polycyclic (I. E., A ring that divides adjacent pairs of carbon atoms) functional groups.

As used herein, the term " heteroaryl group "means that the aryl group contains 1 to 3 heteroatoms selected from the group consisting of N, O, S and P, and the remainder is carbon. When the heteroaryl group is a fused ring, it may contain 1 to 3 heteroatoms in each ring.

More specifically, the substituted or unsubstituted C6 to C30 aryl group and / or the substituted or unsubstituted C2 to C30 heteroaryl group may be substituted or unsubstituted phenyl group, substituted or unsubstituted naphthyl group, substituted or unsubstituted anthra A substituted or unsubstituted phenanthryl group, a substituted or unsubstituted naphthacenyl group, a substituted or unsubstituted pyrenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted p-terphenyl group, a substituted or unsubstituted naphthacenyl group, A substituted or unsubstituted aryl group, a substituted m-terphenyl group, a substituted or unsubstituted chrysenyl group, a substituted or unsubstituted triphenylenyl group, a substituted or unsubstituted perylenyl group, a substituted or unsubstituted indenyl group, a substituted or unsubstituted furanyl group , A substituted or unsubstituted thiophenyl group, a substituted or unsubstituted pyrrolyl group, a substituted or unsubstituted pyrazolyl group, a substituted or unsubstituted imidazolyl group, a substituted or unsubstituted triazolyl group, a substituted or unsubstituted pyrazolyl group, A substituted or unsubstituted thiazolyl group, a substituted or unsubstituted oxadiazolyl group, a substituted or unsubstituted thiadiazolyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted pyrimidinyl group , A substituted or unsubstituted pyrazinyl group, a substituted or unsubstituted triazinyl group, a substituted or unsubstituted benzofuranyl group, a substituted or unsubstituted benzothiophenyl group, a substituted or unsubstituted benzimidazolyl group, a substituted or unsubstituted benzothiophenyl group, A substituted or unsubstituted quinolinyl group, a substituted or unsubstituted quinazolinyl group, a substituted or unsubstituted quinazolinyl group, a substituted or unsubstituted quinoxalinyl group, a substituted or unsubstituted naphthyridinyl group , A substituted or unsubstituted benzoxazine group, a substituted or unsubstituted benzothiazine group, a substituted or unsubstituted acridinyl group, a substituted or unsubstituted phenazine group, a substituted or unsubstituted A substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted dibenzothiophenyl group, , Or a combination thereof, but are not limited thereto.

In the present specification, a single bond means a bond directly connected to a carbon atom or a carbon atom other than a carbon atom or a hetero atom other than carbon. Specifically, when L is a single bond, the substituent connected to L is directly connected to the center core, . That is, it does not mean a methylene group linked through carbon.

In the present specification, the hole property means a property of facilitating the injection into the light emitting layer and the movement in the light emitting layer of the hole formed in the anode due to conduction characteristics along the HOMO level. More specifically, it may be similar to the characteristic of pushing electrons.

Further, the electron characteristic means a property of facilitating the injection of electrons formed in the anode into the luminescent layer and the movement in the luminescent layer due to conduction characteristics along the LUMO level. More specifically, it may be similar to the characteristic of attracting electrons.

In one embodiment of the present invention, a compound for an organic optoelectronic device represented by the following Formula 1 can be provided.

[Chemical Formula 1]

In Formula 1,

A ¹ and A ² are each independently N, O, S or NL ⁴ -R ⁴ , and at least one of A ¹ and A ² is N or NL ⁴ -R ⁴ ,

X is O, S, SO ₂ (O═S═O), PO (P═O), NL ⁵ -R ⁵ , CR R ', or SiR R'

R ¹ to R ⁵ , R and R 'are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C3 to C30 heterocyclo An alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 heteroaryl group, a substituted or unsubstituted amine group, a substituted or unsubstituted C6 to C30 arylamine group, a substituted or unsubstituted C6 to C30 heteroarylamine groups, substituted or unsubstituted C1 to C30 alkoxy groups, substituted or unsubstituted C2 to C30 alkoxycarbonyl groups, substituted or unsubstituted C2 to C30 alkoxycarbonylamino groups, substituted or unsubstituted C7 to C30 alkoxycarbonyl groups, C30 aryloxycarbonylamino group, a substituted or unsubstituted C1 to C30 sulfamoylamino group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, a substituted Substituted or unsubstituted C3 to C40 silyl groups, substituted or unsubstituted C3 to C40 silyloxy groups, substituted or unsubstituted C1 to C30 acyl groups, substituted or unsubstituted C1 to C20 acyloxy groups, substituted or unsubstituted A substituted or unsubstituted C1 to C30 acylamino group, a substituted or unsubstituted C1 to C30 sulfonyl group, a substituted or unsubstituted C1 to C30 alkylthiol group, a substituted or unsubstituted C1 to C30 heterocyclic thiol group, a substituted or unsubstituted C6 to C30 A halogen atom, a halogen-containing group, a cyano group, a hydroxyl group, an amino group, a nitro group, a carboxyl group, a cyano group, A perovskenyl group, or a combination thereof,

R ¹ and R ² are each independently present or fused together to form a ring,

Each of L ¹ to L ⁵ independently represents a single bond, a substituted or unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted C3 to C30 cycloalkylene group, a substituted or unsubstituted C3 to C30 heterocycloalkylene group, An unsubstituted C6 to C30 arylene group, or a substituted or unsubstituted C3 to C30 heteroarylene group, a substituted or unsubstituted C6 to C30 arylene amine group, a substituted or unsubstituted C6 to C30 heteroarylene amine group, A substituted or unsubstituted C1 to C30 alkoxysylene group, a substituted or unsubstituted C1 to C30 aryloxylene group, a substituted or unsubstituted C2 to C30 alkenylene group, a substituted or unsubstituted C2 to C30 alkynylene group, It is a combination of these.

The compound for an organic optoelectronic device according to an embodiment of the present invention has both an electron characteristic and a hole characteristic at the same time and has an amphoteric characteristic, so that an appropriate T1 value and excellent thermal stability can be obtained.

In addition, the compound represented by Formula 1 may be a compound having various energy bandgaps by introducing various substituents.

By using a compound having an appropriate energy level according to the substituent of the compound in an organic optoelectronic device, the hole transporting ability or the electron transporting ability is enhanced to have an excellent effect in terms of efficiency and driving voltage, and excellent electrochemical and thermal stability. The lifetime characteristics can be improved when the device is driven.

More specifically, the formula (1) may be represented by any one of the following formulas (2) to (5).

[Chemical Formula 2] < EMI ID =

,

,

,

,

,

,

,

,

In the general formulas (2) to (5), the definitions of X, R ¹ to R ⁴ and L ¹ to L ⁴ are as described above.

Specifically, R ¹ to R ⁴ may each independently be hydrogen, a substituted or unsubstituted silyl group, or a substituted or unsubstituted functional group listed in Group I below.

[Group I]

In said group I,

Each Z is independently N or CR ^a ,

Y is CR ^b R ^c , SiR ^d R ^e or NR ^f ,

Wherein R ^a to R ^f are each independently selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C3 to C30 heterocycloalkyl group, A substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 heteroaryl group, a substituted or unsubstituted amine group, a substituted or unsubstituted C6 to C30 arylamine group, a substituted or unsubstituted C6 to C30 heteroaryl An amino group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C2 to C30 alkoxycarbonyl group, a substituted or unsubstituted C2 to C30 alkoxycarbonylamino group, a substituted or unsubstituted C7 to C30 aryloxycarbonyl An amino group, a substituted or unsubstituted C1 to C30 sulfamoylamino group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, A substituted or unsubstituted C1 to C20 acyl group, a substituted or unsubstituted C1 to C20 acyloxy group, a substituted or unsubstituted C1 to C20 acylamino group, a substituted or unsubstituted C1 to C20 acyl group, A substituted or unsubstituted C1 to C30 alkylthiol group, a substituted or unsubstituted C1 to C30 heterocyclothiol group, a substituted or unsubstituted C6 to C30 arylthiol group, a substituted or unsubstituted C1 to C30 arylthiol group, A halogen atom, a halogen-containing group, a cyano group, a hydroxyl group, an amino group, a nitro group, a carboxyl group, a perorenyl group or a substituted or unsubstituted C1 to C30 heteroarylthiol group Lt; / RTI &

* Is a connecting point and may be located in any of the elements forming the functional group.

In addition, the formula (1) may be represented by any one of the following formulas (6) to (12).

[Chemical Formula 7] [Chemical Formula 8] [Chemical Formula 9]

,

,

,

,

,

,

[Chemical Formula 11] [Chemical Formula 12]

,

,

,

,

In the above formulas (6) to (12)

The definitions of A ¹ , A ² , R ¹ to R ³ , and L ¹ to L ³ are as described above.

R ¹ and R ² in the general formulas (10) to (12) may be fused to form a ring.

Wherein L ¹ to L ⁵ each independently represent a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted p-terphenylene group, a substituted or unsubstituted m-terphenylene group, Lt; / RTI > may be a substituted o-terphenylene group,

Examples of the substituted or unsubstituted phenylene group include the following S-1, S-2, and S-3.

[Formula S-1] [Formula S-2] [Formula S-3]

Examples of the substituted or unsubstituted biphenylene group include groups represented by the following formulas S-4, S-5, and S-6.

[Formula S-4] [Formula S-5] [Formula S-6]

Examples of the substituted or unsubstituted p-terphenylene group include the following S-7, S-8, and S-9.

[Formula S-7] [Formula S-8] [Formula S-9]

Examples of the substituted or unsubstituted m-terphenylene group include the following S-10, S-11, S-12, and the like.

[Formula S-10] [Formula S-11] [Formula S-12]

Examples of the substituted or unsubstituted o-terphenylene group include the following S-13, S-14, S-15, and the like.

[Chemical Formula S-13] [Chemical Formula S-14] [Chemical Formula S-15]

In the specific examples of L ¹ to L ⁵ , R ²⁹ to R ³⁴ independently represent hydrogen, deuterium, a halogen group, a hydroxy group, an amino group, a substituted or unsubstituted C1 to C30 amine group, a nitro group, C1 to C10 alkyl groups such as a C1 to C40 silyl group, a C1 to C30 alkyl group, a C1 to C10 alkylsilyl group, a C3 to C30 cycloalkyl group, a C6 to C30 aryl group, a C1 to C20 alkoxy group, a fluoro group, A trifluoroalkyl group or a cyano group.

In one embodiment of the present invention, R ¹ to R ⁵ are selected from the group consisting of a substituted or unsubstituted phenyl group, a substituted or unsubstituted thiazinyl group, a substituted or unsubstituted pyrimidinyl group, a substituted or unsubstituted pyridyl group, A substituted carbazolyl group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted dibenzothiophenyl group.

In one embodiment of the present invention, L ¹ to L ⁵ may be a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, or a substituted or unsubstituted carbazolylene group.

Hereinafter, the organic optoelectronic device to which the compound for an organic optoelectronic device described above is applied will be described.

The organic optoelectronic device is not particularly limited as long as it is an element capable of converting electric energy and optical energy. Examples of the organic optoelectronic device include organic light emitting devices, organic solar cells, and organic photoconductor drums.

Here, an organic light emitting device, which is an example of an organic optoelectronic device, will be described with reference to the drawings.

1 and 2 are cross-sectional views illustrating an organic light emitting device according to an embodiment.

1, an organic optoelectronic device 100 according to an embodiment includes an anode 120 and a cathode 110 facing each other, and an organic layer 105 located between the anode 120 and the cathode 110 .

The anode 120 may be made of a conductor having a high work function to facilitate, for example, hole injection, and may be made of, for example, a metal, a metal oxide, and / or a conductive polymer. The anode 120 is made of a metal such as nickel, platinum, vanadium, chromium, copper, zinc, gold, or an alloy thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); A combination of ZnO and Al or a metal and an oxide such as SnO ₂ and Sb; Conductive polymers such as poly (3-methylthiophene), poly (3,4- (ethylene-1,2-dioxy) thiophene), polypyrrole and polyaniline, It is not.

The cathode 110 may be made of a conductor having a low work function, for example, to facilitate electron injection, and may be made of, for example, a metal, a metal oxide, and / or a conductive polymer. The cathode 110 is made of a metal such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, lead, cesium, barium or the like or an alloy thereof; Layer structure materials such as LiF / Al, LiO ₂ / Al, LiF / Ca, LiF / Al and BaF ₂ / Ca.

The organic layer 105 includes the light emitting layer 130 including the compound for the organic optoelectronic device described above.

The light emitting layer 130 may include, for example, the compound for organic optoelectronic devices described above alone or a mixture of at least two of the compounds for organic optoelectronic devices, . When the compound for the organic optoelectronic device and the compound for the organic optoelectronic device described above are mixed and contained, for example, they may be contained in the form of a host and a dopant, and the compound for the organic optoelectronic device described above may be included as a host, for example. The host may be, for example, a phosphorescent host. The compound can be used as a green phosphorescent host in the luminescent layer.

When the above-mentioned compound for an organic optoelectronic device is contained as a host, the dopant may be an inorganic, organic, or organic compound and may be selected from known dopants.

Referring to FIG. 2, the organic light emitting diode 200 further includes a hole assist layer 140 in addition to the light emitting layer 230. The hole assist layer 140 can further enhance the hole injection and / or hole mobility between the anode 120 and the light emitting layer 230 and block the electrons. The hole-assist layer 140 may be, for example, a hole transport layer, a hole injection layer, and / or an electron blocking layer, and may include at least one layer. The above-described compound for an organic optoelectronic device may be included in the light emitting layer 230 and / or the hole auxiliary layer 140. 1 or 2, the organic thin film layer 105 may further include an electron transport layer, an electron injection layer, a hole injection layer, and the like.

The organic light emitting devices 100 and 200 may be formed by forming an anode or a cathode on a substrate and then performing a dry deposition method such as evaporation, sputtering, plasma plating, and ion plating; Or a wet film formation method such as spin coating, slit coating, dipping, flow coating, and inkjet printing, or the like to form an organic layer thereon, A negative electrode or a positive electrode.

The organic light emitting device described above can be applied to an organic light emitting display.

Hereinafter, specific embodiments of the present invention will be described. However, the embodiments described below are only intended to illustrate or explain the present invention, and thus the present invention should not be limited thereto.

(Preparation of compound for organic optoelectronic device)

Synthetic example  1: Synthesis of compound 1

Compound 1 was synthesized in the same manner as in Reaction Scheme 1 below.

[Reaction Scheme 1]

Step 1: Synthesis of intermediate product (L-1)

87.0 g (730 mmol) of 2-cyanophenol, 124.4 g (745 mmol) of ethyl bromoacetate, 403.8 g (2.92 mol) of potassium carbonate and 1740 mL of acetone were placed in a 3000 mL flask and reacted at 60 ° C for 12 hours. The reaction was terminated by TLC and then cooled to room temperature. Filtered and washed with water and acetone to obtain 150 g (yield: 96.7%) of Intermediate L-1.

Step 2: Synthesis of intermediate product (L-2)

50.0 g (244 mmol) of the intermediate product (L-1) and 500 ml of DMF (dimethylformamide) were stirred at 0 ° C. and 6.43 g (268 mmol) of sodium hydride was added to the 1000 mL flask. Respectively. After confirming the completion of the reaction by TLC, 500 mL of dichloromethane and 2000 mL of distilled water were injected to separate the organic layer, followed by concentration under reduced pressure. 37.0 g (yield 64%) of Intermediate L-2 was obtained.

Step 3: Synthesis of intermediate product (L-3)

23.4 g (114 mmol) of the intermediate L-2, 32 ml (228 mmol) of triethylamine, 0.42 g (3.4 mmol) of 4-dimethylaminopyridine and 230 ml of MC (methylene chloride) were added to a 1000 ml flask, . Dissolve 49.8 g (228 mmol) of di-t-butyl dicarbonate in 100 ml of MC and slowly drop into the above solution. After stirring for 13 hours, the completion of the reaction was confirmed by TLC. After extraction through ethyl acetate, the organic layer was concentrated to obtain 32 g (yield: 91.9%) of intermediate L-3.

Step 4: Synthesis of intermediate product (L-4)

35 g (115 mmol) of Intermediate L-3 and 5.5 g (229 mmol) of lithium hydroxide, 250 ml of water and 700 ml of tetrahydrofuran are placed in a 2000 ml flask and reacted at room temperature for 11 hours. The completion of the reaction was confirmed by TLC. After extraction through ethyl acetate, the organic layer was concentrated to obtain 23 g (yield: 72.4%) of intermediate L-4.

Step 5: Synthesis of intermediate product (L-5)

23 g (83 mmol) of intermediate L-4, 17.8 ml (83 mmol) of diphenylphosphoryl azide, 11.6 ml (83 mmol) of triethylamine and 370 ml of t-butyl alcohol were placed in a 1000 ml flask, The completion of the reaction was confirmed by TLC. After extraction through ethyl acetate, the organic layer was concentrated and 18 g (yield: 62.3%) of intermediate L-5 was obtained via column (EA: n-Hex = 1: 5 v / v).

Step 6: Synthesis of intermediate product (L-6)

In a 100 mL flask, 4.2 mL (12.1 mmol) of the intermediate L-5 (40 mL) was added, and after stirring for 30 minutes, 10 mL of concentrated hydrochloric acid was added and the reaction was completed at room temperature. After completion of the reaction, the reaction mixture is basified with aqueous NaOH solution. After extraction through ethyl acetate, the organic layer was concentrated to obtain 1.3 g (yield: 72.6%) of intermediate L-6.

Step 7: Synthesis of intermediate product (L-7)

In a 100 mL flask, 10 g (67.5 mmol) of intermediate L-6, 8.6 g (81.0 mmol) of benzaldehyde and 27.0 g (113.4 mmol) of sodium persulfate were added to 100 mL of DMF and the reaction was terminated by TLC. After extraction through ethyl acetate, the organic layer was concentrated to obtain 12.1 g (yield: 76.5%) of intermediate L-7.

Step 8: Synthesis of Compound 1

1000 mL flask in the intermediate product L-7 12 g (51.23 mmol ), 9- (4- bromophenyl) -9H- carbazol 18.16 g (56.35 mmol) and _{Pd 2 (dba) 3 1.4g (} 1.54 mmol), 3.6 ml (7.68 mmol) of tri (t-butyl) phosphine (50% toluene), 7.38 g (76.8 mmol) of sodium (t-butoxide) and 120 ml of toluene were added and refluxed under nitrogen gas for 12 hours. The end of the reaction was confirmed by TLC and then cooled. After filtration, wash several times with water and methanol. The resulting solid was dissolved in dichlorobenzene and then recrystallized from methanol to obtain 16 g (yield: 65.7%) of Compound 1.

MS (MALDI-TOF): m / z 475.5 [M] ^< ⁺ & gt ^;

Synthetic example  2: Synthesis of compound 5

(3-bromophenyl) -4,6-diphenyl-1,3,5-triazine was used in place of 9- (4-bromophenyl) -9H- Compound 5 was synthesized through Reaction Scheme 1 in the same manner as in Synthesis Example 1, except that azine was used.

Synthetic example  3: Synthesis of Compound 16

Except that 2- (3-bromophenyl) -4,6-diphenylpyrimidine was used instead of 9- (4-bromophenyl) -9H-carbazole in the eighth step of Synthesis Example 1 , Compound 16 was synthesized through Reaction Scheme 1 in the same manner as Synthesis Example 1.

Synthetic example  4: Synthesis of Compound 19

Compound 19 was synthesized via the same route as shown in Reaction Scheme 2 below.

 [Reaction Scheme 2]

Step 1: Synthesis of intermediate product (M-1)

138.1 g (730 mmol) of 2-bromobenzene thiol, 124.4 g (745 mmol) of ethyl bromoacetate, 403.8 g (2.92 mol) of potassium carbonate and 2760 mL of acetone were placed in a 3000 mL flask and reacted at 60 ° C. for 18 hours . The reaction was terminated by TLC and then cooled to room temperature. Filtered and washed with water and acetone to obtain 173.2 g (yield: 86.2%) of Intermediate M-1.

Step 2: Synthesis of intermediate product (M-2)

50.0 g (244 mmol) of the intermediate product (M-1), 33.2 g (370.7 mmol) of cupric cyanide (CuCN) and 500 ml of DMF were reacted at 160 DEG C for 5 hours in a 1000 mL flask. After confirming the completion of the reaction by TLC, 500 mL of dichloromethane and 2000 mL of distilled water were injected to separate the organic layer, followed by concentration under reduced pressure. 29.5 g (yield: 73.4%) of Intermediate M-2 was obtained.

Step 3 - Step 7

M-2 was reacted in the same manner as in Step 3 of Synthesis Example 1, Step 3, to obtain M-7.

Step 8: Synthesis of Compound 19

1000 mL flask was charged with the intermediate product M-7 10 g (40.0 mmol ), 3- (4- bromophenyl) -9-phenyl -9H- carbazol 17.50 g (43.9 mmol) and Pd ₂ (dba) ₃ 1.1g ( 2.9 ml (5.9 mmol) of tri (t-butyl) phosphine (50% toluene) and 5.8 g (59.9 mmol) of sodium (t-butoxide) and 100 ml of toluene were added. . The end of the reaction was confirmed by TLC and then cooled. After filtration, wash several times with water and methanol. The resulting solid was dissolved in dichlorobenzene and recrystallized from methanol to obtain 17.5 g (yield: 77.2%) of Compound 19.

MS (MALDI-TOF): m / z 567.7 [M] ^< ^{+ &}

Synthetic example  5: Synthesis of Compound 22

(4-bromophenyl) -9-phenyl-9H-carbazole was used in place of 3- (4-bromophenyl) , 5-triazine was used in place of the compound represented by formula (1).

Synthetic example  6: Synthesis of Compound 35

In the eighth step of Synthesis Example 4, 3-bromo-9- (4,6-diphenylpyrimidin-2-yl) carbamate was used instead of 3- (4- ) -9H-carbazole was used in place of the compound represented by the above formula (2).

Specific compounds according to one embodiment of the present invention prepared according to the above synthesis method are shown in Table 1 below.

Central body Substituent a Substituent b Substituent c Material structure MS [M] ^< ^{+ &} compound
number

-

475.54 One

-

551.64 2

-

465.50 3

-

541.60 4

-

541.60 5

-

465.50 6

-

541.60 7

541.60 8

541.60 9

541.60 10

541.60 11

-

475.54 12

-

630.70 13

-

630.70 14

-

630.70 15

-

540.61 16

-

630.70 17

-

491.60 18

-

567.70 19

-

481.57 20

-

557.67 21

-

557.67 22

-

481.57 23

-

557.67 24

557.67 25

557.67 26

557.67 27

557.67 28

-

491.60 29

-

491.60 30

-

646.76 31

-

646.76 32

-

556.68 33

-

645.77 34

-

645.77 35

-

641.83 36

-

717.93 37

-

631.80 38

-

707.89 39

-

707.89 40

-

631.80 41

-

707.89 42

707.89 43

707.89 44

707.89 45

707.89 46

-

641.83 47

-

796.99 48

-

796.99 49

-

786.99 50

706.91 51

-

583.76 52

550.65 53

540.62 54

616.71 55

550.65 56

540.62 57

616.71 58

539.63 59

705.81 60

705.81 61

616.71 62

550.65 63

616.71 64

705.81 65

781.90 66

- -

400.43 67

- -

466.49 68

- -

400.43 69

- -

555.58 70

- -

631.68 71

- -

631.68 72

-

400.43 73

-

555.58 74

-

631.68 75

- -

554.60 76

- -

416.49 77

- -

482.56 78

- -

416.49 79

- -

571.65 80

- -

647.75 81

- -

647.75 82

-

416.49 83

-

571.65 84

-

647.75 85

-

570.66 86

- -

566.72 87

- -

632.78 88

- -

566.72 89

- -

721.88 90

- -

797.97 91

- -

797.97 92

-

566.72 93

-

721.88 94

-

797.97 95

-

475.54 96

-

541.60 97

-

475.54 98

-

630.70 99

-

706.79 100

-

706.79 101

-

630.70 102

-

706.79 103

475.54 104

630.70 105

706.79 106

630.70 107

706.79 108

-

629.71 109

(Fabrication of organic light emitting device)

Comparative Example  One

Specifically, the manufacturing method of the organic light emitting device will be described. An ITO glass substrate having a sheet resistance of 15 Ω / cm ² is cut into a size of 50 mm × 50 mm × 0.7 mm, and is cut with acetone, isopropyl alcohol and pure water For 15 minutes, and then rinsed with UV ozone for 30 minutes.

The prepared HTO transparent electrode was used as an anode to vacuum deposit the HTM compound on the ITO substrate to form a 1200 Å thick hole injection layer.

[HTM]

4,4-N, N-dicarbazolebiphenyl (CBP) was used as a host in the light emitting layer, and phosphorescent green dopant was doped with 7 wt% of PhGD compound to form a 300Å thick light emitting layer. As the anode, ITO was used in a thickness of 1000 Å, and as a cathode, aluminum (Al) was used in a thickness of 1000 Å.

[PhGD]

Then, 50 Å of BAlq [Bis (2-methyl-8-quinolinolato-N1, O8) - (1,1'-Biphenyl-4-olato)] and 250 Å of Alq3 [Tris (8-hydroxyquinolinato) aluminum] Were successively laminated to form an electron transporting layer.

LiF 5 Å and Al 1000 Å were sequentially vacuum-deposited on the electron transport layer to form a cathode, thereby preparing an organic light emitting device.

[BAlq] [Alq3]

Example  One

An organic photoelectric device was fabricated in the same manner as in Comparative Example 1, except that the compound 5 prepared in Synthesis Example 2 was used as the light emitting layer.

Example  2

An organic photoelectric device was fabricated in the same manner as in Comparative Example 1, except that the compound 16 prepared in Synthesis Example 3 was used as the light emitting layer.

Example  3

An organic photoelectric device was fabricated in the same manner as in Comparative Example 1, except that the compound 22 prepared in Synthesis Example 5 was used as the light emitting layer.

Example  4

An organic photovoltaic device was fabricated in the same manner as in Comparative Example 1, except that the compound 35 prepared in Synthesis Example 6 was used as the light emitting layer.

(Performance Measurement of Organic Light Emitting Device)

For each of the organic light emitting devices manufactured in Comparative Example 1 and Examples 1 to 4, the current density change, the luminance change, and the light emitting efficiency were measured according to the voltage. The specific measurement method is as follows, and the results are shown in Table 2 below.

1) Measurement of change of current density with voltage change

For each of the organic light emitting devices manufactured in Comparative Example 1 and Examples 1 to 4, the current value flowing through the unit device was measured using a current-voltage meter (Keithley 2400) while increasing the voltage, and the measured current value And the current density was measured.

2) Measurement of luminance change according to voltage change

For each of the organic light emitting devices manufactured in Comparative Example 1 and Examples 1 to 4, the luminance was measured using a luminance meter (Minolta Cs-1000A) while increasing the voltage.

3) Measurement of luminous efficiency

The luminous efficiency was calculated using the luminance value, the current density and the voltage (V) measured in the above "1) Measurement of change of current density according to voltage change" and "2) Measurement of luminance change with voltage change" Are listed in Table 2, respectively.

4) Measurement of color coordinates

For each of the organic light emitting devices manufactured in Examples 1 to 4 and Comparative Example 1, color coordinates were measured using a luminance meter (Keithley 2635B) at 6000 cd / m ² .

Luminance 6000 cd / m ² Driving voltage
(V) Luminous efficiency
(cd / A) Power efficiency
(lm / W) CIE x y Comparative Example 1 6.70 34.8 16.3 0.360 0.626 Example 1 4.93 50.4 35.7 0.351 0.604 Example 2 4.95 48.0 33.2 0.348 0.607 Example 3 4.72 47.2 35.2 0.346 0.607 Example 4 4.92 50.7 36.1 0.352 0.604

As can be seen from Table 2, the OLEDs of Examples 1 to 4 exhibited improved characteristics in terms of driving voltage and luminous efficiency as compared with Comparative Example 1. [

Specifically, the compound used in the organic light emitting device according to Examples 1 to 4 has a structure that is easy to receive electrons including nitrogen, unlike the compound used in the organic light emitting device according to Comparative Example 1. Accordingly, it can be confirmed that the driving voltage of the organic light emitting device according to the first to fourth embodiments is lower than that of the organic light emitting device according to the first comparative example.

In addition, the compounds used in the organic light emitting devices according to Examples 1 to 4 have a bipolar structure including a structure that is susceptible to holes and a structure that is susceptible to electrons, so that the flow of holes and electrons can be properly balanced, It can be seen that the organic light emitting device according to each of Examples 1 to 4 has higher light emitting efficiency than the organic light emitting device according to Comparative Example 1. [

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the following claims. As will be understood by those skilled in the art. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.

100, 200: organic light emitting device 110: cathode
120: anode 105: organic thin film layer
130, 230: light emitting layer 140: hole transport layer

Claims (13)

A compound for an organic optoelectronic device represented by the following Formula 1:
[Chemical Formula 1]

In Formula 1,
A ¹ and A ² are each independently N or NL ⁴ -R ⁴ ,
X is O or S,
R ¹ to R ⁴ are each independently hydrogen, deuterium, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 heteroaryl group, or a combination thereof,
L ¹ to L ⁴ are each independently a single bond, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C3 to C30 heteroarylene group, or a combination thereof. The method according to claim 1,
Wherein the compound represented by Formula 1 is represented by Formula 2 or Formula 3:
[Chemical Formula 2] < EMI ID =

,

,
Wherein X, R ¹ to R ⁴ and L ¹ to L ⁴ are the same as defined in the above 1. The method according to claim 1,
Wherein R ¹ to R ⁴ are each independently hydrogen or a substituted or unsubstituted functional group listed in Group I:
[Group I]

In said group I,
Each Z is independently N or CR ^a ,
Y is CR ^b R ^c , SiR ^d R ^e or NR ^f ,
Wherein R ^a to R ^f are each independently selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 heteroaryl group, A cyano group, a hydroxyl group, an amino group, a nitro group, a carboxyl group, a ferrocenyl group or a combination thereof,
* Is a connecting point and may be located in any of the elements forming the functional group. The method according to claim 1,
Wherein the compound represented by Formula 1 is represented by any one of the following Chemical Formulas 6 to 12:
[Chemical Formula 7] [Chemical Formula 8] [Chemical Formula 9]

,

,

,

[Chemical Formula 11] [Chemical Formula 12]

,

,

In the above formulas (6) to (12)
A ¹ and A ² are each independently N or NL ⁴ -R ⁴ ,
X is O or S,
R ¹ to R ⁴ are each independently hydrogen, deuterium, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 heteroaryl group, or a combination thereof,
L ¹ to L ⁴ are each independently a single bond, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C3 to C30 heteroarylene group, or a combination thereof. delete The method according to claim 1,
Wherein R ¹ to R ⁴ are selected from the group consisting of a substituted or unsubstituted phenyl group, a substituted or unsubstituted triazinyl group, a substituted or unsubstituted pyrimidinyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted carbazolyl group, Or an unsubstituted dibenzofuranyl group, or a substituted or unsubstituted dibenzothiophenyl group. The method according to claim 1,
Wherein L ¹ to L ⁴ are a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, or a substituted or unsubstituted carbazolylene group. The method according to claim 1,
Wherein the compound represented by Formula 1 is any one of compounds represented by the following Chemical Formulas 1 to 35:
[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]

. The anode, cathode, and
And at least one organic layer positioned between the anode and the cathode,
Wherein the organic layer comprises the compound for an organic optoelectronic device according to any one of claims 1 to 4 and 6 to 8. 10. The method of claim 9,
Wherein the organic layer includes a light emitting layer,
Wherein the light emitting layer comprises the compound for an organic optoelectronic device. 11. The method of claim 10,
Wherein the compound for an organic optoelectronic device is included as a host of the light emitting layer. 10. The method of claim 9,
Wherein the organic layer includes at least one auxiliary layer selected from a hole injection layer, a hole transport layer, an electron blocking layer, an electron transport layer, an electron injection layer and a hole blocking layer,
Wherein the auxiliary layer comprises a compound for the organic optoelectronic device
Organic optoelectronic devices. A display device comprising the organic opto-electronic device according to claim 9.

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