KR20180123660A - Composition and organic optoelectric device and display device - Google Patents

Abstract

The present invention relates to an organic photoelectric device and a display device which include an anode and a cathode facing each other, and at least one layer of an organic layer located between the anode and the cathode The organic layer includes a light emitting layer, and the light emitting layer comprises a first organic compound represented by chemical formula 3, and a second organic compound composed of a combination of a moiety represented by chemical formula 6 and a moiety represented by chemical formula 7. In the chemical formula 3, Z1 to Z13, R1 to R17, and n1 to n4 are as defined in the specification.

Description

Technical Field [0001] The present invention relates to a composition, an organic optoelectronic device,

Compositions, organic optoelectronic devices and display devices.

 An organic optoelectronic diode is an element that can switch between electric energy and light 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. BACKGROUND ART An organic light emitting device is a device that converts electric energy into light by applying an electric current to an organic light emitting material, and typically has a structure in which an organic layer is interposed between an anode and a cathode.

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

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

One embodiment provides a composition for an organic optoelectronic device capable of implementing a high-efficiency and long-lived organic optoelectronic device.

Another embodiment provides an organic optoelectronic device comprising a composition for a scarce organic optoelectronic device.

Another embodiment provides a display device comprising the organic opto-electronic device.

According to one embodiment, there is provided an organic compound represented by the following general formula (1).

[Chemical Formula 1]

In Formula 1,

Z ¹ to Z ¹³ are each independently N or CR ^a ,

At least one of Z ¹ to Z ¹³ is N,

L ¹ is a single bond or a substituted or unsubstituted C6 to C30 arylene group,

R ¹ to R ¹⁰ are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C12 aryl group, or a combination thereof,

R ¹¹ to R ¹⁴ and R ^a are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C12 aryl group, a substituted or unsubstituted C3 to C12 heterocyclic group, Lt; / RTI >

R ¹ to R ¹⁴ and R ^a are each independently present, or two adjacent rings are combined to form a ring,

n1 and n2 are each independently an integer of 0 to 2;

According to another embodiment, there is provided a composition for an organic optoelectronic device comprising a first organic compound, which is the organic compound, and at least one second organic compound, which has a carbazole moiety.

According to another embodiment, the organic light emitting device includes an anode and a cathode facing each other, and at least one organic layer positioned between the anode and the cathode, and the organic layer includes a light emitting layer, and a layer between the anode and the light emitting layer, And an auxiliary layer disposed between the light emitting layers, wherein the light emitting layer or the auxiliary layer comprises the organic compound or the composition for the organic optoelectronic device.

According to another embodiment, there is provided a display device including the organic opto-electronic device.

High-efficiency long-lived organic optoelectronic devices can be realized.

1 is a cross-sectional view illustrating an organic light emitting device according to one embodiment.

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 trifluoro such as a C1 to C40 silyl group, a C1 to C30 alkyl group, a C1 to C10 alkylsilyl group, a C6 to C30 aryl group, a C2 to C30 heterocyclic group, a C1 to C20 alkoxy group, a trifluoromethyl group, An alkyl group or a cyano group.

In one example, " substitution " in the present specification means that at least one of the substituents or the hydrogen in the compound is substituted by deuterium, a substituted or unsubstituted C1 to C30 amine group, a nitro group, a substituted or unsubstituted C1 to C40 silyl group, An alkyl group, a C1 to C10 alkylsilyl group, a C6 to C30 aryl group, or a C2 to C30 heterocyclic group.

In one example, " substitution " in the present specification means that at least one hydrogen in the compound is substituted with deuterium, a substituted or unsubstituted C1 to C40 silyl group, a C1 to C30 alkyl group, a C1 to C10 alkylsilyl group or a C6 to C30 aryl group Lt; / RTI >

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 1 to C 20 amine group, the substituted or unsubstituted C 3 to C 40 silyl group, A C1 to C10 trifluoroalkyl group such as a C1 to C30 aryl group, a C3 to C30 heterocyclic group, a C1 to C20 alkoxy group, and a trifluoromethyl group, or a cyano group may be fused to form a ring. For example, the substituted C6 to C30 aryl group may be fused with another adjacent substituted C6 to C30 aryl group to form a substituted or unsubstituted fluorene ring.

As used herein, unless otherwise defined, it is meant that at least one heteroatom is contained in one functional group and the remainder is carbon. The heteroatom may be selected from N, O, S, P, and Si.

As used herein, " aryl group " means a group having one or more carbocyclic aromatic moieties and broadly refers to carbocyclic aromatic moieties linked by a single bond, and carbocyclic aromatic moieties are referred to as " But also includes non-aromatic fused rings fused indirectly. The aryl groups include monocyclic, polycyclic or fused polycyclic (i. E., Rings that divide adjacent pairs of carbon atoms) functional groups.

As used herein, the term "heterocyclic group" refers to a heterocyclic group having at least one heteroatom selected from N, O, S, P and Si in a ring compound such as an aryl group, a cycloalkyl group, a fused ring thereof, And the remainder is carbon. When the heterocyclic group is a fused ring, the heterocyclic group or the ring may include one or more heteroatoms.

More specifically, the substituted or unsubstituted aryl group and / or the substituted or unsubstituted heterocyclic group may be a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, A substituted or unsubstituted naphthacenyl group, a substituted or unsubstituted pyrenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted quaterphenyl group, a substituted or unsubstituted pyrazinyl group, A substituted or unsubstituted thienyl group, a substituted or unsubstituted thienyl group, a substituted or unsubstituted thienyl group, a substituted or unsubstituted thienyl group, a substituted or unsubstituted thienyl group, a substituted or unsubstituted thienyl group, Or an 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 oxazolyl group, A substituted or unsubstituted thiadiazolyl group, a substituted or unsubstituted pyridinyl group, a substituted or unsubstituted pyrimidinyl group, a substituted or unsubstituted thiadiazolyl group, a substituted or unsubstituted thiadiazolyl group, a substituted or unsubstituted thiadiazolyl group, A substituted or unsubstituted pyrazinyl group, a substituted or unsubstituted thiazinyl group, a substituted or unsubstituted benzofuranyl group, a substituted or unsubstituted benzothiophenyl group, a substituted or unsubstituted benzimidazolyl group, a substituted or unsubstituted indolyl group , A substituted or unsubstituted quinolinyl group, a substituted or unsubstituted isoquinolinyl group, a substituted or unsubstituted quinazolinyl group, a substituted or unsubstituted quinoxalinyl group, a substituted or unsubstituted naphthyridinyl group, a substituted or unsubstituted quinazolinyl group, A substituted or unsubstituted benzothiazyl group, a substituted or unsubstituted acridinyl group, a substituted or unsubstituted phenazinyl group, a substituted or unsubstituted phenothiazine group, a substituted or unsubstituted benzothiazyl group, a substituted or unsubstituted benzothiazyl group, A substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted carbazole group, a combination thereof, or a combination thereof, or a substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted carbazolyl group, May be in a fused form, but are not limited thereto.

In one embodiment of the present invention, the substituted or unsubstituted aryl group is a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted A quaterphenyl group or a substituted or unsubstituted fluorenyl group.

In one embodiment of the present invention, a substituted or unsubstituted indenyl group, a substituted or unsubstituted pyridinyl group, a substituted or unsubstituted pyrimidinyl group, a substituted or unsubstituted pyrazinyl group, a substituted or unsubstituted triazinyl group , A substituted or unsubstituted indolyl group, a substituted or unsubstituted quinolinyl group, a substituted or unsubstituted isoquinolinyl group, a substituted or unsubstituted quinazolinyl group, a substituted or unsubstituted quinoxalinyl group, a substituted or unsubstituted quinolinyl group, A substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted carbazole group, a combination thereof, or a combination thereof may be fused, but the present invention is not limited thereto.

In the present specification, the hole property refers to a property of forming holes by donating electrons when an electric field is applied, and has a conduction property along the HOMO level so that the injection of holes formed in the anode into the light emitting layer, Quot; refers to the property of facilitating the movement of the hole formed in the light emitting layer to the anode and the movement of the hole in the light emitting layer.

In addition, the electron characteristic refers to a characteristic that electrons can be received when an electric field is applied. The electron characteristic has a conduction characteristic along the LUMO level to inject electrons formed in the cathode into the light emitting layer, move electrons formed in the light emitting layer to the cathode, It is a characteristic that facilitates movement.

The organic compounds according to one embodiment will be described below.

The organic compound according to one embodiment may be represented by the following formula (1).

[Chemical Formula 1]

In Formula 1,

Z ¹ to Z ¹³ are each independently N or CR ^a ,

At least one of Z ¹ to Z ¹³ is N,

L ¹ is a single bond or a substituted or unsubstituted C6 to C30 arylene group,

R ¹ to R ¹⁰ are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C12 aryl group, or a combination thereof,

R ¹¹ to R ¹⁴ and R ^a are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C12 aryl group, a substituted or unsubstituted C3 to C12 heterocyclic group, Lt; / RTI >

R ¹ to R ¹⁴ and R ^a are each independently present, or two adjacent rings are combined to form a ring,

n1 and n2 are each independently an integer of 0 to 2;

Since the organic compound includes a dibenzoquinoxaline moiety and a ring having at least one nitrogen, it can be a structure that is easily susceptible to electrons when an electric field is applied, and accordingly, the driving voltage of the organic optoelectronic device Can be lowered and the efficiency can be increased.

The LUMO energy of the organic compound calculated by the B3LYP / 6-31G ** method using Gaussian 09 may be, for example, -1.5 eV to -2.0 eV. Within this range, for example, it may be about 1.7 eV to -1.8 eV.

In addition, the organic compound includes a nitrogen-containing ring substituent extending to one side of dibenzoquinoxaline, thereby realizing an asymmetric structure, thereby inhibiting the interaction of molecules and lowering the crystallinity.

In addition, since the organic compound has an asymmetric structure, the stacking of molecules can be effectively prevented, thereby improving the process stability and lowering the deposition temperature.

In the above formula (1), at least two of Z ¹ to Z ¹³ may be N, for example.

In Formula 1, at least three of Z ¹ to Z ¹³ may be N, for example.

In Formula 1, at least one of Z ¹ to Z ³ may be N, for example.

At least one of Z ¹ to Z ³ may be N and each of Z ⁴ to Z ¹³ may independently be CR ^a wherein R ^a is hydrogen, An alkyl group, a substituted or unsubstituted C6 to C12 aryl group, a substituted or unsubstituted C3 to C12 heterocyclic group, or a combination thereof.

In the above formula (1), at least two of Z ¹ to Z ³ may be N, for example.

In Formula 1, for example, at least two of Z ¹ to Z ³ may be N and Z ⁴ to Z ¹³ each independently may be N or CR ^a , wherein R ^a is hydrogen, deuterium, substituted or unsubstituted C1 C10 alkyl group, a substituted or unsubstituted C6 to C12 aryl group, a substituted or unsubstituted C3 to C12 heterocyclic group, or a combination thereof.

In Formula 1, for example, Z ¹ to Z ³ may all be N, and Z ⁴ to Z ¹³ each independently may be N or CR ^a , wherein R ^a is hydrogen, deuterium, C10 alkyl group, a substituted or unsubstituted C6 to C12 aryl group, a substituted or unsubstituted C3 to C12 heterocyclic group, or a combination thereof.

In the general formula (1), R ¹ to R ⁴ may be, for example, each independently hydrogen, deuterium or a substituted or unsubstituted C1 to C10 alkyl group, and R ¹ to R ⁴ may be, for example, each independently hydrogen.

In Formula 1, L ¹ may be, for example, a single bond or may have at least one kink structure. Here, the bending structure refers to a structure in which two connecting portions do not form a linear structure. For example, in the case of a phenylene group, o-phenylene and m-phenylene, P-phenylene, which has a bending structure and has a straight-line connecting portion, has no bending structure.

In Formula 1, L ¹ is, for example, a single bond, a substituted or unsubstituted phenylene group having a bending structure, a substituted or unsubstituted biphenylene group having a bending structure, a substituted or unsubstituted terphenylene group having a bending structure, A substituted or unsubstituted quaterphenylene group, and a substituted or unsubstituted pentaphenylene group having a bidentate structure.

In Formula 1, L ¹ may include, for example, a single bond, at least one of a substituted or unsubstituted o-phenylene group and a substituted or unsubstituted m-phenylene group.

In formula (1), L ¹ may be, for example, a single bond or a substituted or unsubstituted group listed in group 1 below.

[Group 1]

In the group 1,

R ³⁰ to R ⁵⁷ are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted A substituted or unsubstituted C6 to C30 arylamine group, a substituted or unsubstituted C6 to C30 heteroarylamine group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C2 to C30 heterocyclic group, a substituted or unsubstituted amine group, , A halogen atom, a cyano group, a hydroxyl group, an amino group, a nitro group, a carboxyl group, a ferrocenyl group, or a combination thereof.

The molecular weight of the organic compound may be, for example, about 750 or less. Within this range, it may be at least about 538 and less than 750. By having the molecular weight in the above range, the thermal decomposition of the organic compound due to the high temperature during the deposition process can be reduced and the heat resistance can be improved. Within this range, it may be about 538 to 749, within this range it may be about 550 to 730, and within this range it may be about 600 to 700.

The organic compound may be represented, for example, by the following formula (2).

(2)

In Formula 2,

Z ¹ to Z ¹³ , R ¹ to R ¹⁴ , n ¹ and n 2 are as defined above,

R ¹⁵ to R ¹⁷ are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C12 aryl group, a substituted or unsubstituted C3 to C12 heterocyclic group, Can,

n3 and n4 each independently may be an integer of 0 to 2;

In the above formula (2), for example, n1 + n2 + n3 + n4?

In Formula 2, at least two of Z ¹ to Z ¹³ may be N, for example.

In Formula 2, at least three of Z ¹ to Z ¹³ may be N, for example.

In Formula 2, at least one of Z ¹ to Z ³ may be N, for example.

In Formula 2, for example, at least one of Z ¹ to Z ³ may be N, and each of Z ⁴ to Z ¹³ may independently be CR ^a , wherein R ^a is hydrogen, deuterium, substituted or unsubstituted C 1 to C 10 An alkyl group, a substituted or unsubstituted C6 to C12 aryl group, a substituted or unsubstituted C3 to C12 heterocyclic group, or a combination thereof.

In Formula 2, at least two of Z ¹ to Z ³ may be N, for example.

In Formula 2, for example, at least two of Z ¹ to Z ³ may be N, and each of Z ⁴ to Z ¹³ may independently be N or CR ^a , wherein R ^a is hydrogen, deuterium, substituted or unsubstituted C1 C10 alkyl group, a substituted or unsubstituted C6 to C12 aryl group, a substituted or unsubstituted C3 to C12 heterocyclic group, or a combination thereof.

In Formula 2, for example, Z ¹ to Z ³ may all be N, and Z ⁴ to Z ¹³ may each independently be N or CR ^a , wherein R ^a is hydrogen, deuterium, C10 alkyl group, a substituted or unsubstituted C6 to C12 aryl group, a substituted or unsubstituted C3 to C12 heterocyclic group, or a combination thereof.

In Formula 2, R ¹ to R ⁴ may be, for example, each independently hydrogen, deuterium or a substituted or unsubstituted C1 to C10 alkyl group, and R ¹ to R ⁴ may be, for example, independently hydrogen.

The organic compound may be represented by, for example, the following formula (3) or (4).

(3)

[Chemical Formula 4]

In the above formula (3) or (4), Z ¹ to Z ¹³ , R ¹ to R ¹⁷ , and n1 to n4 are as described above.

In the above formula (3) or (4), for example, n1 + n2 + n3 + n4?

In the above formula (3) or (4), for example, at least two of Z ¹ to Z ¹³ may be N.

In the above formula (3) or (4), at least three of Z ¹ to Z ¹³ may be N, for example.

In the above formula (3) or (4), for example, at least one of Z ¹ to Z ³ may be N.

In Formula 3 or 4, for example, at least one of Z ¹ to Z ³ may be N, and each of Z ⁴ to Z ¹³ may independently be CR ^a , wherein R ^a is hydrogen, deuterium, substituted or unsubstituted C1 C10 alkyl group, a substituted or unsubstituted C6 to C12 aryl group, a substituted or unsubstituted C3 to C12 heterocyclic group, or a combination thereof.

In the above formula (3) or (4), for example, at least two of Z ¹ to Z ³ may be N.

In the above formula 3 or 4, for example, at least two of Z ¹ to Z ³ may be N, and Z ⁴ to Z ¹³ each independently may be N or CR ^a , wherein R ^a is hydrogen, deuterium, A substituted or unsubstituted C6 to C12 aryl group, a substituted or unsubstituted C3 to C12 heterocyclic group, or a combination thereof.

In the above formula 3 or 4, for example, Z ¹ to Z ³ may all be N, and Z ⁴ to Z ¹³ each independently may be N or CR ^a , wherein R ^a is hydrogen, deuterium, A C1 to C10 alkyl group, a substituted or unsubstituted C6 to C12 aryl group, a substituted or unsubstituted C3 to C12 heterocyclic group, or a combination thereof.

In the above formula (3) or (4), R ¹ to R ⁴ may be, for example, each independently hydrogen, deuterium or a substituted or unsubstituted C1 to C10 alkyl group, and R ¹ to R ⁴ may be, for example, each independently hydrogen.

The organic compound may be one of the compounds listed in the following Group 2, but is not limited thereto.

[Group 2]

The above-described organic compounds can be applied to organic optoelectronic devices.

The above-described organic compounds can be applied to organic optoelectronic devices alone or together with other organic compounds. When the above-mentioned organic compound is used together with other organic compounds, it can be applied in the form of a composition.

Hereinafter, one example of the composition for an organic optoelectronic device including the above-described organic compound will be described.

One example of the composition for the organic optoelectronic device may be a composition comprising the above-mentioned organic compound and at least one organic compound having a carbazole moiety. Hereinafter, the organic compound described above is referred to as a 'first organic compound', and at least one organic compound having a carbazole moiety is referred to as a 'second organic compound'.

The second organic compound may be, for example, a compound represented by the following general formula (5).

[Chemical Formula 5]

In Formula 5,

Y ¹ represents a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C2 to C20 alkenylene group, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C2 to C30 divalent A heterocyclic group or a combination thereof,

Ar ¹ is a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heterocyclic group, or a combination thereof,

R ⁶⁰ to R ⁶³ each independently represent hydrogen, deuterium, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C50 aryl group, a substituted or unsubstituted C2 to C50 heterocyclic group, or combinations thereof ,

At least one of R ⁶⁰ to R ⁶³ and Ar ¹ includes a substituted or unsubstituted triphenylene group or a substituted or unsubstituted carbazolyl group.

The second organic compound represented by Formula 5 may be represented by at least one of the following Formulas 5-1 to 5-III.

[Chemical Formula 5-I] [Chemical Formula 5-II]

[Chemical Formula 5-III]

In Formulas 5-I to 5-III,

Y ¹ , Y ⁴ and Y ⁵ are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C2 to C20 alkenylene group, a substituted or unsubstituted C6 to C30 arylene group, a substituted Or an unsubstituted C2 to C30 divalent heterocyclic group or a combination thereof,

Ar ¹ And Ar ⁴ are each independently a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heterocyclic group, or a combination thereof,

R ⁶⁰ to R ⁶³ and R ⁶⁸ to R ⁷⁹ are A substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C50 aryl group, a substituted or unsubstituted C2 to C50 heterocyclic group, or a combination thereof.

The second organic compound represented by Formula 5 may be, for example, a compound listed in Group 3, but is not limited thereto.

[Group 3]

*

The second organic compound may be, for example, a compound consisting of a combination of a moiety represented by the following formula (6) and a moiety represented by the following formula (7).

[Chemical Formula 6] < EMI ID =

In the above formula (6) or (7)

Y ² and Y ³ are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C2 to C20 alkenylene group, a substituted or unsubstituted C6 to C30 arylene group, Or a C2 to C30 divalent heterocyclic group or a combination thereof,

Ar ² and Ar ³ are each independently a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heterocyclic group, or a combination thereof,

R ⁶⁴ to R ⁶⁷ are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C50 aryl group, a substituted or unsubstituted C2 to C50 heterocyclic group, or combinations thereof ,

The adjacent two * in the above formula (6) form a fused ring by combining with the two ^f * in the above formula (7). In the above formula (6), * without each fused ring is independently CR ^b , wherein R ^b is hydrogen, , A substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C12 aryl group, a substituted or unsubstituted C3 to C12 heterocyclic group, or a combination thereof.

The second organic compound composed of the combination of the moiety represented by Formula 6 and the moiety represented by Formula 7 may be selected from the compounds listed in the following Group 4, but is not limited thereto.

[Group 4]

The second organic compound may include at least one compound selected from the group consisting of the compound represented by the formula (5) and the moiety represented by the formula (6) and the moiety represented by the formula (7).

The composition may include the first organic compound and the second organic compound in a weight ratio of about 1:10 to 10: 1.

The composition may be applied to an organic layer of an organic optoelectronic device, and the first organic compound and the second organic compound may serve as a host. In this case, the first organic compound may be a compound having a bipolar characteristic having a relatively strong electron characteristic, and the second organic compound may have a bipolar characteristic having a relatively strong hole characteristic. The second organic compound may be used together with the first organic compound, By improving the stability, the luminous efficiency and lifetime characteristics can be further improved.

The composition may further include at least one organic compound in addition to the first organic compound and the second organic compound.

The composition may further comprise a dopant. The dopant may be a red, green or blue dopant, for example a phosphorescent dopant.

The dopant may be a metal complex that emits light by multiple excitation that is excited by a triplet state or higher, and is a substance that emits light by mixing with the first host compound and the second host compound. May be used. The dopant may be, for example, an inorganic, organic, or organic compound, and may include one or more species.

Examples of the phosphorescent dopant include organic metal compounds including Ir, Pt, Os, Ti, Zr, Hf, Eu, Tb, Tm, Fe, Co, Ni, Ru, Rh and Pd or combinations thereof. The phosphorescent dopant may be, for example, a compound represented by the following formula (Z), but is not limited thereto.

(Z)

L ₂ MX

In the above formula (Z), M is a metal, L and X are the same or different from each other and are ligands that complex with M.

M may be Ir, Pt, Os, Ti, Zr, Hf, Eu, Tb, Tm, Fe, Co, Ni, Ru, Rh, Pd or combinations thereof, Lt; / RTI >

The composition may be formed into a thin film by a dry film forming method or a solution process. The dry film forming method may be, for example, a chemical vapor deposition method, sputtering, plasma plating, or ion plating, and two or more compounds may be simultaneously deposited or a compound having the same deposition temperature may be mixed to form a film. The solution process may be, for example, ink jet printing, spin coating, slit coating, bar coating and / or dip coating.

Hereinafter, the organic compound or the organic optoelectronic device to which the above-described composition 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.

The organic optoelectronic device may include an anode and a cathode facing each other, and at least one organic layer positioned between the anode and the cathode, and the organic layer may include the organic compound described above or the composition described above.

In one example, the organic layer may include the organic compound or a light emitting layer including the composition.

For example, the organic layer may include a light emitting layer, an auxiliary layer located between the anode and the light emitting layer and / or between the cathode and the light emitting layer, and the auxiliary layer may include the organic compound or the composition.

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

1 is a cross-sectional view illustrating an organic light emitting device according to one embodiment.

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

The anode 110 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 110 may be 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 120 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 120 may be formed 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 above-described organic compound or the light emitting layer 130 including the above-described composition.

The light emitting layer 130 may include the organic compound or the composition as a host and may include the organic compound alone or may be a mixture of at least two of the organic compounds described above, Or may contain a mixture of the above-mentioned organic compounds or the above-mentioned compositions with other organic compounds.

The light emitting layer 130 may further include a dopant. The dopant may be a red, green or blue dopant, for example a phosphorescent dopant. The dopant is as described above.

The organic layer 105 may further include an auxiliary layer (not shown) positioned between the anode 110 and the light emitting layer 130 and / or between the cathode 120 and the light emitting layer 130. The auxiliary layer may be a hole injection layer, a hole transporting layer, an electron blocking layer, an electron injecting layer, an electron transporting layer, a hole blocking layer, or a combination thereof. The auxiliary layer may comprise the above-described organic compounds or the above-described compositions.

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.

Synthesis of intermediates

Synthetic example  1: Synthesis of intermediate I-1

[Reaction Scheme 1]

In a nitrogen atmosphere, 3-bromophenanthrene-9,10-dione (100 g, 348 mmol) from zhengzhou chemical international Co., Ltd. (http://www.chemicalintl.com/) was dissolved in 1 L of ethanol. Ethylenediamine (25.1 g, 418 mmol) was added thereto, and the mixture was heated under reflux for 8 hours. Acetic acid was further added to the flask in an amount of 1.5 L and heated at reflux for 9 hours. After completion of the reaction, the reaction solution was cooled to room temperature. The resulting solid was filtered and washed with excess ethanol to give Intermediate I-1 (78.5 g, 73%).

HRMS (70 eV, EI +): m / z calcd for C16H9BrN2: 307.9949, found: 308.

Elemental Analysis: C, 62%; H, 3%

Synthetic example  2: Synthesis of intermediate I-2

[Reaction Scheme 2]

(70 g, 226 mmol) was dissolved in 0.6 L of tetrahydrofuran (THF) in a nitrogen atmosphere and then 3-chlorophenylboronic acid (42.5 g, 272 mmol) and tetrakis (triphenylphosphine) palladium (2.61 g, 2.26 mmol ) Were added and stirred. Saturated water-saturated potassium carbonate (78.1 g, 565 mmol) was added and heated at 80 ° C for 8 hours to reflux. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO 4, followed by filtration and concentration under reduced pressure. The obtained residue was purified by flash column chromatography to obtain intermediate I-2 (65.5 g, 85%).

HRMS (70 eV, EI +): m / z calcd for C22H13ClN2: 340.0767, found: 340.

Elemental Analysis: C, 78%; H, 4%

Synthetic example  3: Synthesis of Intermediate I-3

[Reaction Scheme 3]

Bis (pinacolato) diboron (53.6 g, 211 mmol) and (1,1'-bis (diphenylphosphine)) were dissolved in 0.6 L of dimethylformamide (DMF) ferrocene dichloropalladium (II) (1.44 g, 1.76 mmol) and potassium acetate (51.8 g, 528 mmol) were added and heated at 150 ° C for 20 hours to reflux. After completion of the reaction, water was added to the reaction solution, the mixture was filtered, and then dried in a vacuum oven. The thus-obtained residue was purified by flash column chromatography to obtain Intermediate I-3 (51.7 g, 68%).

HRMS (70 eV, EI +): m / z calcd for C28H25BN2O2: 432.2009, found: 432.

Elemental Analysis: C, 78%; H, 6%

Synthetic example  4: Synthesis of intermediate I-4

[Reaction Scheme 4]

1-bromo-3-iodobenzene (39.3 g, 139 mmol) and tetrakis (triphenylphosphine) palladium (1.34 g, 0.1 mmol) were dissolved in 0.45 L of tetrahydrofuran , 1.16 mmol) were added and stirred. Saturated potassium salt of potassium carbonate (40.1 g, 290 mmol) was added to the reaction mixture, and the mixture was heated at 80 ° C for 5 hours to reflux. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO 4, followed by filtration and concentration under reduced pressure. The thus-obtained residue was purified by flash column chromatography to obtain Intermediate I-4 (47.1 g, 88%).

HRMS (70 eV, EI +): m / z calcd for C28H17BrN2: 460.0575, found: 460.

Elemental Analysis: C, 73%; H, 4%

Synthetic example  5: Synthesis of intermediate I-5

[Reaction Scheme 5]

Bis (pinacolato) diboron (26.4 g, 104 mmol) and (1,1'-bis (diphenylphosphine)) were dissolved in 0.3 L of dimethylformamide (DMF) ferrocene dichloropalladium (II) (0.71 g, 0.87 mmol) and potassium acetate (25.5 g, 260 mmol) were added and the mixture was refluxed by heating at 150 ° C for 6 hours. After completion of the reaction, water was added to the reaction solution, the mixture was filtered, and then dried in a vacuum oven. The thus obtained residue was purified by flash column chromatography to obtain intermediate I-5 (34.8 g, 79%).

HRMS (70 eV, EI +): m / z calcd for C34H29BN2O2: 508.2322, found: 508.

Elemental Analysis: C, 80%; H, 6%

Synthetic example  6: Synthesis of Intermediate I-6

[Reaction Scheme 6]

Bis (pinacolato) diboron (98.6 g, 388 mmol) and 1,1'-bis (diphenylphosphine) were dissolved in 1 L of dimethylformamide (DMF) ferrocene) dichloropalladium (II) (2.64 g, 3.23 mmol) and potassium acetate (95.1 g, 969 mmol) were added and the mixture was refluxed by heating at 150 ° C for 5 hours. After completion of the reaction, water was added to the reaction solution, the mixture was filtered, and then dried in a vacuum oven. The obtained residue was purified by flash column chromatography to obtain intermediate I-6 (104 g, 90%).

HRMS (70 eV, EI +): m / z calcd for C22H21BN2O2: 356.1696, found: 356.

Elemental Analysis: C, 74%; H, 6%

Synthetic example  7: Synthesis of Intermediate I-7

[Reaction Scheme 7]

1-bromo-2-iodobenzene (95.3 g, 337 mmol) and tetrakis (triphenylphosphine) palladium (3.25 g, 337 mmol) were dissolved in 1 L of tetrahydrofuran (THF) 2.81 mmol) were added and stirred. Saturated water-saturated potassium carbonate (97.1 g, 703 mmol) was added and the mixture was refluxed by heating at 80 ° C for 8 hours. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO 4, followed by filtration and concentration under reduced pressure. The thus-obtained residue was purified by flash column chromatography to obtain Intermediate I-7 (92.0 g, 85%).

HRMS (70 eV, EI +): m / z calcd for C22H13BrN2: 384.0262, found: 384.

Elemental Analysis: C, 69%; H, 3%

Synthetic example  8: Synthesis of Intermediate I-8

[Reaction Scheme 8]

(70.8 g, 280 mmol) and tetrakis (triphenylphosphine) palladium (2.70 g, 2.34 mmol) were dissolved in 0.7 L of tetrahydrofuran (THF) in a nitrogen atmosphere and the intermediate I- ) Were added and stirred. Potassium hydroxide (80.9 g, 585 mmol), which was saturated with water, was added and the mixture was refluxed by heating at 80 ° C for 12 hours. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO 4, followed by filtration and concentration under reduced pressure. The obtained residue was purified by flash column chromatography to obtain Intermediate I-8 (81.0 g, 83%).

HRMS (70 eV, EI +): m / z calcd for C28H17ClN2: 416.1080, found: 416.

Elemental Analysis: C, 81%; H, 4%

Synthetic example  9: Synthesis of intermediate I-9

[Reaction Scheme 9]

Bis (pinacolato) diboron (54.8 g, 216 mmol) and (1,1'-bis (diphenylphosphine) ferrocene) were dissolved in 1 L of dimethylformamide (DMF) ) dichloropalladium (II) (1.47 g, 1.80 mmol) and potassium acetate (53.0 g, 540 mmol) were added and the mixture was refluxed by heating at 150 ° C for 23 hours. After completion of the reaction, water was added to the reaction solution, the mixture was filtered, and then dried in a vacuum oven. The thus-obtained residue was purified by flash column chromatography to obtain Intermediate I-9 (55.8 g, 61%).

HRMS (70 eV, EI +): m / z calcd for C34H29BN2O2: 508.2322, found: 508.

Elemental Analysis: C, 80%; H, 6%

Synthetic example  10: Synthesis of intermediate I-10

[Reaction Scheme 10]

1-bromo-2-iodobenzene (39.3 g, 139 mmol) and tetrakis (triphenylphosphine) palladium (1.34 g, 0.1 mmol) were dissolved in 0.45 L of tetrahydrofuran , 1.16 mmol) were added and stirred. Saturated water-saturated potassuim carbonate (40.1 g, 290 mmol) was added and the mixture was refluxed by heating at 80 ° C for 8 hours. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO 4, followed by filtration and concentration under reduced pressure. The residue thus obtained was purified by flash column chromatography to obtain intermediate I-10 (48.2 g, 90%).

HRMS (70 eV, EI +): m / z calcd for C28H17BrN2: 460.0575, found: 460.

Elemental Analysis: C, 73%; H, 4%

Synthetic example  11: Synthesis of Intermediate I-11

[Reaction Scheme 11]

Bis (pinacolato) diboron (29.7 g, 117 mmol) and (1,1'-bis (diphenylphosphine) diphenylphosphine) were dissolved in 0.4 L of dimethylformamide (DMF) ferrocene) dichloropalladium (II) (0.80 g, 0.98 mmol) and potassium acetate (28.7 g, 293 mmol) were added and heated at 150 ° C for 18 hours to reflux. After completion of the reaction, water was added to the reaction solution, the mixture was filtered, and then dried in a vacuum oven. The thus-obtained residue was purified by flash column chromatography to obtain Intermediate I-11 (32.2 g, 65%).

HRMS (70 eV, EI +): m / z calcd for C34H29BN2O2: 508.2322, found: 508.

Elemental Analysis: C, 80%; H, 6%

Synthetic example  12: Synthesis of intermediate I-12

[Reaction Scheme 12]

Intermediate I-5 (40 g, 78.7 mmol) was dissolved in 0.3 L of tetrahydrofuran (THF) in a nitrogen atmosphere and then 1-bromo-3-iodobenzene (26.7 g, 94.4 mmol) and tetrakis (triphenylphosphine) palladium , 0.79 mmol) were added and stirred. Saturated potassium salt of potassium carbonate (27.2 g, 197 mmol) was added and the mixture was refluxed by heating at 80 ° C for 8 hours. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO 4, followed by filtration and concentration under reduced pressure. The thus-obtained residue was purified by flash column chromatography to obtain intermediate I-12 (37.6 g, 89%).

HRMS (70 eV, EI +): m / z calcd for C34H21BrN2: 536.0888, found: 536.

Elemental Analysis: C, 76%; H, 4%

Synthetic example  13: Synthesis of intermediate I-13

[Reaction Scheme 13]

Bis (pinacolato) diboron (17.0 g, 67.0 mmol) and (1,1'-bis (diphenylphosphine)) were dissolved in 0.2 L of dimethylformamide (DMF) ferrocene dichloropalladium (II) (0.46 g, 0.56 mmol) and potassium acetate (16.4 g, 167 mmol) were added and the mixture was refluxed by heating at 150 ° C for 6 hours. After completion of the reaction, water was added to the reaction solution, the mixture was filtered, and then dried in a vacuum oven. The thus-obtained residue was purified by flash column chromatography to obtain intermediate I-13 (26.7 g, 82%).

HRMS (70 eV, EI +): m / z calcd for C40H33BN2O2: 584.2635, found: 584.

Elemental Analysis: C, 82%; H, 6%

Synthetic example  14: Synthesis of Intermediate I-14

[Reaction Scheme 14]

3,6-dibromophenanthrene-9,10-dione (100 g, 273 mmol) from zhengzhou chemical international Co., Ltd. (100 g, 273 mmol) was dissolved in 1 L of ethanol in a nitrogen atmosphere, Ethylenediamine (25.1 g, 418 mmol) was added, and the mixture was refluxed by heating for 8 hours. Then acetic acid was further added in 1.5 L and heated for 9 hours to reflux. After completion of the reaction, the reaction solution was cooled to room temperature. The resulting solid was filtered and washed with excess ethanol to give Intermediate I-14 (78.5 g, 73%).

HRMS (70 eV, EI +): m / z calcd for C16H8Br2N2: 385.9054, found: 385.

Elemental Analysis: C, 50%; H, 2%

Synthetic example  15: Synthesis of intermediate I-15

[Reaction Scheme 15]

2-bromo-5-iodopyridine (100 g, 352 mmol) from Sigma Aldrich (http://www.sigmaaldrich.com/) was dissolved in 0.8 L of tetrahydrofuran (THF) in a nitrogen atmosphere, pyridin-4-ylboronic (52.0 g, 423 mmol) and tetrakis (triphenylphosphine) palladium (4.07 g, 3.52 mmol) were added and stirred. Saturated water-saturated potassuim carbonate (122 g, 880 mmol) was added and heated at 80 ° C for 12 hours to reflux. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO 4, followed by filtration and concentration under reduced pressure. The residue thus obtained was purified by flash column chromatography to obtain intermediate I-15 (29.8 g, 36%).

HRMS (70 eV, EI +): m / z calcd for C10H7BrN2: 233.9793, found: 234.

Elemental Analysis: C, 51%; H, 3%

Synthesis of final compound

Synthetic example  16: Synthesis of compound 1

[Reaction Scheme 16]

Intermediate I-3 (10 g, 23.1 mmol) was dissolved in 0.1 L of tetrahydrofuran (THF) in a nitrogen atmosphere, and then it was purchased from Nanjing Kindchem Co., Ltd. (http://www.kindchem.net/) 4-chloro-2,6-diphenylpyridine (6.15 g, 23.1 mmol) and tetrakis (triphenylphosphine) palladium (0.27 g, 0.23 mmol) were added and stirred. Saturated water-saturated potassuim carbonate (7.98 g, 57.8 mmol) was added and heated at 80 ° C for 10 hours to reflux. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO 4, followed by filtration and concentration under reduced pressure. The residue thus obtained was separated and purified by flash column chromatography to obtain Compound 1 (11.1 g, 90%).

HRMS (70 eV, EI +): m / z Calcd for C39H25N3: 535.2048, found: 535.

Elemental Analysis: C, 87%; H, 5%

Synthetic example  17: Synthesis of Compound 2

[Reaction Scheme 17]

Intermediate I-3 (10 g, 23.1 mmol) was dissolved in 0.1 L of tetrahydrofuran (THF) in a nitrogen atmosphere, followed by addition of 2-chloro- 4,6-diphenylpyrimidine (6.16 g, 23.1 mmol) and tetrakis (triphenylphosphine) palladium (0.27 g, 0.23 mmol) were added and stirred. Saturated water-saturated potassuim carbonate (7.98 g, 57.8 mmol) was added and heated at 80 ° C for 10 hours to reflux. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO 4, followed by filtration and concentration under reduced pressure. The residue thus obtained was separated and purified by flash column chromatography to obtain Compound 2 (10.5 g, 85%).

HRMS (70 eV, EI +): m / z calcd for C38H24N4: 536.2001, found: 536.

Elemental Analysis: C, 85%; H, 5%

Synthetic example  18: Synthesis of Compound 3

[Reaction Scheme 18]

Intermediate I-3 (10 g, 23.1 mmol) was dissolved in 0.1 L of tetrahydrofuran (THF) in a nitrogen atmosphere, followed by addition of 2-chloro- 4,6-diphenyl-1,3,5-triazine (6.18 g, 23.1 mmol) and tetrakis (triphenylphosphine) palladium (0.27 g, 0.23 mmol) were added and stirred. Saturated water-saturated potassuim carbonate (7.98 g, 57.8 mmol) was added and heated at 80 ° C for 10 hours to reflux. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO 4, followed by filtration and concentration under reduced pressure. The residue thus obtained was separated and purified by flash column chromatography to obtain Compound 3 (11.5 g, 93%).

HRMS (70 eV, EI +): m / z calcd for C37H23N5: 537.1953, found: 537.

Elemental Analysis: C, 83%; H, 4%

Synthetic example  19: Synthesis of Compound (12)

[Reaction Scheme 19]

Intermediate I-5 (10 g, 19.7 mmol) was dissolved in 0.1 L of tetrahydrofuran (THF) in a nitrogen atmosphere, followed by addition of 2-chloro- 4,6-diphenyl-1,3,5-triazine (5.27 g, 19.7 mmol) and tetrakis (triphenylphosphine) palladium (0.23 g, 0.20 mmol) were added and stirred. Saturated water-saturated potassuim carbonate (6.81 g, 49.3 mmol) was added and heated at 80 ° C for 9 hours to reflux. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO 4, followed by filtration and concentration under reduced pressure. The residue thus obtained was separated and purified by flash column chromatography to obtain Compound 12 (9.67 g, 80%).

HRMS (70 eV, EI +): m / z calcd for C43H27N5: 613.2266, found: 613.

Elemental Analysis: C, 84%; H, 4%

Synthetic example  20: Synthesis of Compound 21

[Reaction Scheme 20]

Intermediate I-9 (10 g, 19.7 mmol) was dissolved in 0.1 L of tetrahydrofuran (THF) in a nitrogen atmosphere, followed by addition of 2-chloro- 4,6-diphenyl-1,3,5-triazine (5.27 g, 19.7 mmol) and tetrakis (triphenylphosphine) palladium (0.23 g, 0.20 mmol) were added and stirred. Saturated water-saturated potassuim carbonate (6.81 g, 49.3 mmol) was added and heated at 80 ° C for 12 hours to reflux. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO 4, followed by filtration and concentration under reduced pressure. The residue thus obtained was separated and purified by flash column chromatography to obtain Compound 21 (9.31 g, 77%).

HRMS (70 eV, EI +): m / z calcd for C43H27N5: 613.2266, found: 613.

Elemental Analysis: C, 84%; H, 4%

Synthetic example  21: Synthesis of Compound 30

[Reaction Scheme 21]

Intermediate I-11 (10 g, 19.7 mmol) was dissolved in 0.1 L of tetrahydrofuran (THF) in a nitrogen atmosphere, followed by addition of 2-chloro- 4,6-diphenyl-1,3,5-triazine (5.27 g, 19.7 mmol) and tetrakis (triphenylphosphine) palladium (0.23 g, 0.20 mmol) were added and stirred. Saturated water-saturated potassium carbonate (6.81 g, 49.3 mmol) was added and the mixture was refluxed by heating at 80 ° C for 10 hours. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO 4, followed by filtration and concentration under reduced pressure. The residue thus obtained was separated and purified by flash column chromatography to obtain Compound 30 (6.29 g, 52%).

HRMS (70 eV, EI +): m / z calcd for C43H27N5: 613.2266, found: 613.

Elemental Analysis: C, 84%; H, 4%

Synthetic example  22: Synthesis of Compound 39

[Reaction Scheme 22]

Intermediate I-13 (10 g, 17.1 mmol) was dissolved in 0.1 L of tetrahydrofuran (THF) in a nitrogen atmosphere, followed by the addition of 2-chloro- 4,6-diphenyl-1,3,5-triazine (4.58 g, 17.1 mmol) and tetrakis (triphenylphosphine) palladium (0.20 g, 0.17 mmol) were added and stirred. Saturated water-saturated potassium carbonate (5.92 g, 42.8 mmol) was added and heated at 80 ° C for 15 hours to reflux. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO 4, followed by filtration and concentration under reduced pressure. The residue thus obtained was separated and purified by flash column chromatography to obtain Compound 39 (10.6 g, 90%).

HRMS (70 eV, EI +): m / z calcd for C49 H31 N5: 689.2579, found: 689.

Elemental Analysis: C, 85%; H, 5%

Synthetic example  23: Synthesis of Compound Host 1

Was synthesized in the same manner as in Synthesis Example 17 of the published patent KR2014-0135524A.

HRMS (70 eV, EI +): m / z calcd for C45 H29 N3: 611.2361, found: 611.

Elemental Analysis: C, 88%; H, 5%

Synthetic example  24: Compound Host2  synthesis

[Reaction Scheme 23]

Intermediate I-15 (12.1 g, 51.5 mmol) and tetrakis (triphenylphosphine) palladium (0.60 g, 0.52 mmol) were dissolved in 0.1 L of tetrahydrofuran (THF) ) Were added and stirred. Potassium carbonate (17.8 g, 129 mmol) saturated with water was added and the mixture was refluxed by heating at 80 ° C for 18 hours. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO 4, followed by filtration and concentration under reduced pressure. The residue thus obtained was separated and purified by flash column chromatography to obtain a compound Host 2 (10.4 g, 75%).

HRMS (70 eV, EI +): m / z calcd for C36 H22 N6: 538.1906, found: 538.

Elemental Analysis: C, 80%; H, 4%

Fabrication of Organic Light Emitting Device I

Example  One

Compound 1 obtained in Synthesis Example 16 was used as a host and Ir (PPy) 3 was used as a dopant to prepare an organic light emitting device.

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. Specifically, an explanation will be given of a method of manufacturing an organic light emitting device. 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 in acetone, isopropyl alcohol and pure water After ultrasonic cleaning for 15 minutes, UV ozone cleaning was used for 30 minutes.

N4, N4'-di (naphthalen-1-yl) -N4, N4'-diphenylbiphenyl-4,4'-diamine ( NPB) (80 nm) was deposited thereon to form a hole transporting layer of 800 ANGSTROM. Subsequently, using the compound 1 obtained in Synthesis Example 16 under the same vacuum deposition condition, a light emitting layer having a thickness of 300 angstroms was formed. Ir (PPy) 3, which is a phosphorescent dopant, was simultaneously deposited thereon. At this time, the deposition rate of the phosphorescent dopant was adjusted so that the phosphorescent dopant content was 7% by weight when the total amount of the light emitting layer was 100% by weight.

Bis (2-methyl-8-quinolinolate) -4- (phenylphenolato) aluminum (BAlq) was deposited on the light emitting layer using the same vacuum deposition conditions to form a hole blocking layer having a thickness of 50 Å. Subsequently, Alq3 was deposited under the same vacuum deposition conditions to form an electron transport layer having a film thickness of 200 ANGSTROM. LiF and Al were sequentially deposited as an anode on the electron transport layer to prepare an organic photoelectric device.

 The structure of the organic photoelectric device was ITO / NPB (80 nm) / EML (Compound 1 (93 wt%) + Ir (PPy) 3 (7 wt%), 30 nm) / Balq (5 nm) / Alq3 ) / LiF (1 nm) / Al (100 nm).

Example  2 to 7

Compound 2 obtained in Synthesis Example 17, Compound 3 obtained in Synthesis Example 18, Compound 12 obtained in Synthesis Example 19, Compound 21 obtained in Synthetic Example 20, Compound 30 obtained in Synthetic Example 21, and Synthesis Example Organic light-emitting devices of Examples 2 to 7 were fabricated in the same manner as in Example 1 except that Compound 39 obtained in Example 22 was used.

Comparative Example  1 to 3

The organic light emitting devices of Comparative Examples 1 to 3 were prepared in the same manner as in Example 1 except that CBP instead of Compound 1 obtained in Synthesis Example 16, Compound 1 obtained in Synthesis Example 23, and Host 2 obtained in Synthesis Example 24 were used, respectively. .

The structures of NPB, BAlq, CBP and Ir (PPy) ₃ used in the production of the organic light emitting device are as follows.

Evaluation I

The current density change, the luminance change, and the light emitting efficiency of the organic light emitting device according to Examples 1 to 7 and Comparative Examples 1 to 3 were measured according to the voltage.

The specific measurement method is as follows, and the results are shown in Table 1.

(1) Measurement of change in current density with voltage change

For the organic light emitting device manufactured, the current flowing through the unit device was measured using a current-voltmeter (Keithley 2400) while raising the voltage from 0 V to 10 V, and the measured current value was divided by the area to obtain the result.

(2) Measurement of luminance change according to voltage change

For the organic light-emitting device manufactured, luminance was measured using a luminance meter (Minolta Cs-1000A) while increasing the voltage from 0 V to 10 V, and the result was obtained.

(3) Measurement of luminous efficiency

The current efficiency (cd / A) at the same current density (10 mA / cm 2) was calculated using the luminance, current density and voltage measured from the above (1) and (2).

No. compound The driving voltage (V) Color (EL color) Efficiency (cd / A) Example 1 One 3.5 Green 88.9 Example 2 2 3.3 Green 90.4 Example 3 3 3.2 Green 98.8 Example 4 12 3.8 Green 85.2 Example 5 21 3.6 Green 83.5 Example 6 30 3.6 Green 88.0 Example 7 39 4.0 Green 85.0 Comparative Example 1 CBP 4.8 Green 31.4 Comparative Example 2 HOST1 4.2 Green 74.3 Comparative Example 3 HOST2 4.3 Green 18.5

Referring to Table 1, it can be seen that the organic light emitting devices according to Examples 1 to 7 have lower driving voltage and higher light emitting efficiency than the organic light emitting devices according to Comparative Examples 1 to 3.

analysis

The deposition temperature, glass transition temperature (Tg) and high temperature purity of the compound 3 obtained in Synthesis Example 18, the compound 12 obtained in Synthesis Example 19, and the Host 2 obtained in Synthesis Example 24 were respectively measured.

The specific measurement method is as follows, and the results are shown in Table 2.

(1) Deposition process temperature

Means a temperature at which the HOST of the light emitting layer is measured during the manufacturing process of the organic light emitting device according to the first embodiment, and a thickness of 1 ANGSTROM per 1 second (sec) (Å / sec)

(2) Glass transition temperature (Tg)

The energy input difference was measured as a function of temperature while varying the temperature of the sample and reference using a DSC1 instrument from Metter Teledo.

(3) Room temperature purity

(HPLC: model name: Alliance e2695-4 gradient pump) and waters PDA (model name: 2994). The column tube used was Symmetry C18 (3.9 x 150 mm, 5 탆).

(4) High temperature purity

1 g of a sample of the compound was sampled, the glass container was filled with nitrogen and sealed. The purity of the glass container was measured in the same manner as in the method of storing the glass container in an oven at 200 ° C for 200 hours and then measuring the purity at room temperature.

No. No. Deposition process temperature (캜) Tg (占 폚) Room temperature purity (%) High temperature purity (%) Synthesis Example 18
(Example 3) Compound 3 201 103 100 99.99 Synthesis Example 19
(Example 4) Compound 12 216 115 100 99.99 Synthesis Example 24
(Comparative Example 3) Host 2 230.5 88.5 100 98.51

Referring to Table 2, it can be seen that the HOST 2 obtained in Synthesis Example 24 has a low glass transition temperature, a high deposition temperature and a low high temperature purity as compared with the compound 3 obtained in Synthesis Example 18 and the compound 12 obtained in Synthesis Example 19 . Thus, in the case of Comparative Example 3 in which HOST 2 obtained in Synthesis Example 24 was applied to an organic light emitting device, problems were observed in the thin film at the sealing process (at about 60 to 90 ° C) And it is expected that it was affected by heat by the heat generated in the process of manufacturing the glass light emitting device.

On the other hand, the compound 3 obtained in Synthesis Example 18 and the compound 12 obtained in Synthesis Example 19 had a higher molecular weight than the HOST 2 obtained in Synthesis Example 24, but had a low glass transition temperature and were controlled at an appropriate deposition temperature, It can be confirmed that high purity can be maintained.

Fabrication of Organic Light Emitting Device II

Example  8

Glass substrate coated with ITO (Indium tin oxide) thin film with thickness of 1500Å was washed with distilled water ultrasonic wave. After the distilled water was washed, the substrate was ultrasonically cleaned with a solvent such as isopropyl alcohol, acetone, or methanol, dried, and transferred to a plasma cleaner. Then, the substrate was cleaned using oxygen plasma for 10 minutes, and then the substrate was transferred to a vacuum evaporator. Compound A was vacuum deposited on the ITO substrate using the prepared ITO transparent electrode as an anode to form a hole injection layer having a thickness of 700 Å, Compound B was deposited on the injection layer to a thickness of 50 Å, 1020 A thick to form a hole transport layer. The compound 12 obtained in Synthesis Example 19 and the known compound C-10 were used as a host at the same time, and 10 wt% of dopant tropyl tris (2-phenylpyridine) iridium (III) [Ir (ppy) 3] Doped and vacuum evaporated to form a 400 Å thick light emitting layer. Compound 12 and compound B-1 were used in a 1: 1 ratio. Subsequently, Compound D and Liq were simultaneously vacuum-deposited on the light emitting layer at a ratio of 1: 1 to form an electron transport layer having a thickness of 300 Å. Liq 15 Å and Al 1200 Å were sequentially vacuum deposited on the electron transport layer to form a cathode, Respectively.

The organic light emitting device has a structure having five organic thin film layers. Specifically, the organic light emitting device has the following structure.

Compound D: Ir (ppy) 3 = X: X: 10%] (400 Å) / Compound A (700 Å) / Compound B (50 Å) / Compound C (1020 Å) Liq (300 Å) / Liq (15 Å) / Al (1200 Å). (X = weight ratio)

Compound A: N4, N4'-diphenyl-N4, N4'-bis (9-phenyl-9H-carbazol-3-yl) biphenyl-

Compound B: 1,4,5,8,9,11-hexaazatriphenylene-hexacarbonitrile (HAT-CN),

Compound C: N- (biphenyl-4-yl) -9,9-dimethyl- N- (4- (9-phenyl-9H-carbazol-

Compound D: 8- (4- (4,6-di (naphthalen-2-yl) -1,3,5-triazin- 2- yl) phenyl) quinoline

Example  9-13

The organic light emitting devices of Examples 9 to 13 were obtained in the same manner as in Example 8 except that the known compounds B-10, B-31, B-34, B-43 and E- Respectively.

Comparative Example  4 to 9

Compound C-10 was used as a single host instead of the two kinds of compounds 12 and C-10, Compound B-10 was used as a sole host, Compound B-31 was used as a sole host, Compound B-34 was used as a sole host The organic light emitting devices of Comparative Examples 4 to 9 were fabricated in the same manner as in Example 8 except that the compound B-43 was used as a single host and the compound E-1 was used as a single host.

Evaluation II

The luminous efficiency and lifetime characteristics of the organic luminescent devices according to Examples 8 to 13 and Comparative Examples 4 to 9 were evaluated.

The specific measurement method is as follows, and the results are shown in Table 3.

(1) Measurement of change in current density with voltage change

For the organic light emitting device manufactured, the current flowing through the unit device was measured using a current-voltmeter (Keithley 2400) while raising the voltage from 0 V to 10 V, and the measured current value was divided by the area to obtain the result.

(2) Measurement of luminance change according to voltage change

For the organic light-emitting device manufactured, luminance was measured using a luminance meter (Minolta Cs-1000A) while increasing the voltage from 0 V to 10 V, and the result was obtained.

(3) Measurement of luminous efficiency

The current efficiency (cd / A) at the same current density (10 mA / cm 2) was calculated using the luminance, current density and voltage measured from the above (1) and (2).

(4) Life measurement

The time at which the luminance (cd / m ² ) was maintained at 6000 cd / m ² and the current efficiency (cd / A) decreased to 97% was measured and the results were obtained.

The first host Second host The luminous efficiency (cd / A) Lifetime T97 (h) Example 8 Compound 12 C-10 49.5 150 Example 9 Compound 12 B-10 50.0 125 Example 10 Compound 12 B-31 48.1 126 Example 11 Compound 12 B-34 48.5 150 Example 12 Compound 12 B-43 51.0 140 Example 13 Compound 12 E-1 51.0 110 Reference example Compound 12 48.5 100 Comparative Example 4 C-10 16.5 10 Comparative Example 5 B-10 37.5 10 Comparative Example 6 B-31 2.5 0 Comparative Example 7 B-34 18.3 0 Comparative Example 8 B-43 2.8 10 Comparative Example 9 E-1 1.4 30

Referring to Table 3, it can be seen that the organic light emitting devices according to Examples 8 to 13 have significantly improved luminous efficiency and lifetime characteristics as compared with the organic light emitting devices according to Comparative Examples 4 to 9. In addition, the organic light emitting devices according to Examples 8 to 13 have improved luminous efficiency and lifetime compared with the organic light emitting device according to the reference example.

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: Organic light emitting device
105: organic layer
110: anode
120: cathode
130: light emitting layer

Claims (8)

A first organic compound represented by the following formula (3), and
A second organic compound composed of a combination of a moiety represented by the following formula (6) and a moiety represented by the following formula
Wherein the organic photovoltaic device comprises:
(3)

In Formula 3,
Z ¹ to Z ¹³ are each independently N or CR ^a ,
At least one of Z ¹ to Z ³ is N,
R ¹ to R ⁵ and R ⁷ to R ¹⁰ are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C12 aryl group or a combination thereof,
R ¹¹ to R ¹⁷ and R ^a are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C12 aryl group or a substituted or unsubstituted C3 to C12 heterocyclic group, Lt; / RTI >
R ¹ to R ¹⁴ and R ^a are each independently present, or two adjacent rings are combined to form a ring,
n1 and n4 are each independently an integer of 0 to 2,
n1 + n2 + n3 + n4? 2,
[Chemical Formula 6] < EMI ID =

In the above formula (6) or (7)
Y ² and Y ³ are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C2 to C20 alkenylene group, a substituted or unsubstituted C6 to C30 arylene group, Or a C2 to C30 divalent heterocyclic group or a combination thereof,
Ar ² and Ar ³ are each independently a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heterocyclic group, or a combination thereof,
R ⁶⁴ to R ⁶⁷ are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C50 aryl group, a substituted or unsubstituted C2 to C50 heterocyclic group, or combinations thereof ,
The adjacent two * in the above formula (6) form a fused ring by combining with the two ^f * in the above formula (7). In the above formula (6), * without each fused ring is independently CR ^b , wherein R ^b is hydrogen, , A substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C12 aryl group, a substituted or unsubstituted C3 to C12 heterocyclic group, or a combination thereof.
The method of claim 1,
And R ¹ to R ⁴ are each independently hydrogen, deuterium, or a substituted or unsubstituted C1 to C10 alkyl group.
The method of claim 1,
And at least three of Z ¹ to Z ¹³ are N.
The method of claim 1,
Two or three of Z ¹ to Z ³ are N,
Z ⁴ to Z ¹³ are each independently N or CR ^a wherein R ^a is hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C12 aryl group, a substituted or unsubstituted C3 To C12 heterocyclic groups, or combinations thereof.
The method of claim 1,
Wherein the first organic compound is one of the compounds listed in Group 2 below.
[Group 2]

The method of claim 1,
Wherein the second organic compound is one selected from the compounds listed in Group 4 below.
[Group 4]

The anode and the cathode facing each other, and
At least one organic layer positioned between the anode and the cathode
/ RTI >
The organic layer
A light emitting layer, and
And an auxiliary layer disposed between the anode and the light emitting layer or between the cathode and the light emitting layer,
The organic optoelectronic device according to claim 1, wherein the light emitting layer or the auxiliary layer comprises the composition for organic optoelectronic devices according to claim 1.
8. A display device comprising the organic opto-electronic device according to claim 7.

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