阅读说明：本技术 有机光电二极管和显示设备 (Organic photodiode and display device ) 是由 赵平锡 金东映 柳东完 李炳官 郑成显 许达灏 于 2018-06-15 设计创作，主要内容包括：本发明提供了一种有机光电二极管和显示设备,该有机光电二极管包括：彼此面对的阴极和阳极；位于阴极和阳极之间的至少一个有机层,其中该有机层包括有机光电二极管组合物,其包含由化学式1和2的组合表示的第一有机光电二极管化合物,和由化学式3表示的第二有机光电二极管化合物；以及最大发射波长为570-750nm的掺杂剂。化学式1-3的详细描述与说明书中定义的相同。(The present invention provides an organic photodiode and a display device, the organic photodiode including: a cathode and an anode facing each other; at least one organic layer positioned between the cathode and the anode, wherein the organic layer includes an organic photodiode composition comprising a first organic photodiode compound represented by the combination of chemical formulas 1 and 2, and a second organic photodiode compound represented by chemical formula 3; and a dopant having a maximum emission wavelength of 570-750 nm. The detailed descriptions of chemical formulas 1 to 3 are the same as defined in the specification.)

1. An organic opto-electronic device comprising:

an anode and a cathode facing each other, and

at least one organic layer disposed between the anode and the cathode,

wherein the organic layer includes a composition for an organic photoelectric device, the composition comprising a first compound for an organic photoelectric device represented by a combination of chemical formula 1 and chemical formula 2 and a second compound for an organic photoelectric device represented by chemical formula 3; and a dopant having a maximum emission wavelength of 570nm to 750 nm:

wherein, in chemical formulas 1 to 3,

x is O or S, and X is O or S,

t is a substituted or unsubstituted C6-C18 aryl, substituted or unsubstituted dibenzofuranyl, or substituted or unsubstituted dibenzothiophenyl,

ar is a substituted or unsubstituted C6 to C30 aryl group,

L、Y ¹and Y ²Independently a single bond, or a substituted or unsubstituted C6 to C20 arylene group,

two adjacent ones of chemical formula 1 are connected to chemical formula 2,

in chemical formula 1, not linked to chemical formula 2 is independently CR ^a，

R ^aAnd R ¹To R ¹²Independently hydrogen, deuterium, cyano, substituted or unsubstituted C1 to C20 alkyl, or substituted or unsubstituted C6 to C18 aryl,

R ¹³to R ²²Independently hydrogen, deuterium, cyano, amino, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C6 to C18 aryl, or substituted or unsubstituted carbazolyl,

R ¹³to R ²²Independently present or adjacent groups thereof are linked to each other to form a substituted or unsubstituted aromatic ring or a substituted or unsubstituted heteroaromatic ring, and

when R is ¹³To R ²²Independently of each other, R ¹³To R ²²Is a substituted or unsubstituted C6 to C18 aryl group, or a substituted or unsubstituted carbazolyl group.

2. The organic optoelectronic device of claim 1, wherein

The second compound for the organic photoelectric device had 1500mA/cm measured at a voltage of 7V in the following HOD (hole only device) ²To 2500mA/cm ²Current density of (2):

ITO/Compound C

Compound C: n- (biphenyl-4-yl) -9, 9-dimethyl-N- (4- (9-phenyl-9H-carbazol-3-yl) phenyl) -9H-fluoren-2-amine.

3. The organic optoelectronic device of claim 1, wherein

The difference between the HOMO energy levels of the first compound for the organic opto-electronic device and the second compound for the organic opto-electronic device is from 0.2eV to 0.5 eV.

4. The organic optoelectronic device according to claim 1, wherein the maximum emission wavelength of a mixture of the first compound for the organic optoelectronic device and the second compound for the organic optoelectronic device is from 450nm to 550 nm.

5. The organic optoelectronic device according to claim 1, wherein the first compound for the organic optoelectronic device is represented by chemical formula 1B or chemical formula 1C:

wherein, in chemical formulas 1B to 1C,

x is O or S, and X is O or S,

t is a substituted or unsubstituted C6-C18 aryl, substituted or unsubstituted dibenzofuranyl, or substituted or unsubstituted dibenzothiophenyl,

ar is a substituted or unsubstituted C6 to C30 aryl group,

L、Y ¹and Y ²Independently a single bond, or a substituted or unsubstituted C6 to C20 arylene group, and

R ^a1to R ^a4And R ¹To R ⁷Independently hydrogen, deuterium, cyano, substituted or unsubstituted C1 to C20 alkyl, or substituted or unsubstituted C6 to C18 aryl.

6. The organic photoelectric device according to claim 5, wherein chemical formula 1B is represented by chemical formula 1B-2 or chemical formula 1B-3:

wherein, in chemical formula 1B-2 and chemical formula 1B-3,

x is O or S, and X is O or S,

t is a substituted or unsubstituted C6-C18 aryl, substituted or unsubstituted dibenzofuranyl, or substituted or unsubstituted dibenzothiophenyl,

ar is a substituted or unsubstituted C6 to C30 aryl group,

L、Y ¹and Y ²Independently a single bond, or a substituted or unsubstituted C6 to C20 arylene group, and

R ¹to R ⁷Independently hydrogen, deuterium, cyano, substituted or unsubstituted C1 to C20 alkyl, or substituted or unsubstituted C6 to C18 aryl.

7. The organic optoelectronic device according to claim 5, wherein chemical formula 1C is represented by chemical formula 1C-2 or chemical formula 1C-3:

wherein, in chemical formula 1C-2 and chemical formula 1C-3,

x is O or S, and X is O or S,

t is a substituted or unsubstituted C6-C18 aryl, substituted or unsubstituted dibenzofuranyl, or substituted or unsubstituted dibenzothiophenyl,

ar is a substituted or unsubstituted C6 to C30 aryl group,

L、Y ¹and Y ²Independently a single bond, or a substituted or unsubstituted C6 to C20 arylene group, and

R ¹to R ⁷Independently hydrogen, deuterium, cyano, substituted or unsubstituted C1 to C20 alkyl, or substituted or unsubstituted C6 to C18 aryl.

8. The organic optoelectronic device of claim 1, wherein

T is a substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted terphenyl, substituted or unsubstituted dibenzofuranyl or substituted or unsubstituted dibenzothiophenyl group,

ar is substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl or substituted or unsubstituted terphenyl,

L、Y ¹and Y ²Independently a single bond, a substituted or unsubstituted phenylene group, or a substituted or unsubstituted biphenylene group, and

R ¹to R ⁷Independently hydrogen, substituted or unsubstituted C1 to C5 alkyl, or substituted or unsubstituted phenyl.

9. The organic optoelectronic device according to claim 1, wherein the second compound for the organic optoelectronic device is represented by chemical formula 3A-1:

[ chemical formula 3A-1]

Wherein, in chemical formula 3A-1,

R ⁸to R ¹²Independently hydrogen, deuterium, cyano, substituted or unsubstituted C1 to C20 alkyl, or substituted or unsubstituted C6 to C18 aryl,

R ¹³to R ¹⁷Independently hydrogen, deuterium, cyano, amino, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C6 to C18 aryl, or substituted or unsubstituted carbazolyl,

R ¹³to R ¹⁷Independently present or adjacent groups thereof are linked to each other to form a substituted or unsubstituted aromatic ring or a substituted or unsubstituted heteroaromatic ring, and

R ²⁰is a substituted or unsubstituted C6 to C18 aryl group, or a substituted or unsubstituted carbazolyl group.

10. The organic optoelectronic device of claim 9, wherein R ²⁰Is a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted phenanthrenyl group, a substituted or unsubstituted triphenylenyl group, or a substituted or unsubstituted carbazolyl group.

11. The organic optoelectronic device according to claim 9, wherein the first compound for the organic optoelectronic device is represented by chemical formula 1B-2 or chemical formula 1C-2:

wherein, in chemical formula 1B-2 and chemical formula 1C-2,

x is O or S, and X is O or S,

t is a substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted terphenyl, substituted or unsubstituted dibenzofuranyl or substituted or unsubstituted dibenzothiophenyl group,

ar is substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, or substituted or unsubstituted terphenyl,

L、Y ¹and Y ²Independently a single bond, a substituted or unsubstituted phenylene group, or a substituted or unsubstituted biphenylene group, and

R ¹to R ⁷Independently hydrogen, substituted or unsubstituted C1 to C5 alkyl, or substituted or unsubstituted phenyl.

12. The organic optoelectronic device of claim 1, wherein

The organic layer includes a light emitting layer, and

the composition for the organic photoelectric device is included as a host of the light emitting layer.

13. A display device comprising the organic optoelectronic device of any one of claims 1 to 12.

Technical Field

The invention discloses an organic photoelectric device and a display device.

Background

An organic opto-electronic device is a device that converts electrical energy into light energy and vice versa.

Organic photoelectric devices can be classified according to their driving principle as follows. One is an optoelectronic device in which excitons are generated from light energy, separated into electrons and holes, and transferred to different electrodes to generate electric energy, and the other is a light-emitting device in which voltage or current is supplied to the electrodes to generate light energy from the electric energy.

Examples of the organic photodiode may be an organic photoelectric device, an organic light emitting diode, an organic solar cell, and an organic photoconductor drum.

Among them, as the demand for flat panel displays increases, Organic Light Emitting Diodes (OLEDs) have recently attracted attention. An organic light emitting diode is a device that converts electrical energy into light by applying current to an organic light emitting material, and has a structure in which an organic layer is disposed between an anode and a cathode. Here, the organic layer may include a light emitting layer and an optional auxiliary layer, and the auxiliary layer may be, for example, at least one layer selected from a hole injecting layer, a hole transporting layer, an electron blocking layer, an electron transporting layer, an electron injecting layer, and a hole blocking layer.

The performance of the organic light emitting diode may be influenced by the characteristics of the organic layer, and among others, may be mainly influenced by the characteristics of the organic material of the organic layer.

In particular, it is required to develop an organic material capable of increasing hole and electron mobilities while increasing electrochemical stability so that the organic light emitting diode can be applied to a large flat panel display.

Disclosure of Invention

[ problem ] to

One embodiment provides an organic opto-electronic device having high efficiency and long lifetime.

Yet another embodiment provides a display device including an organic optoelectronic device.

[ solution ]

According to one embodiment, an organic photoelectric device includes an anode and a cathode facing each other and at least one organic layer disposed between the anode and the cathode, wherein the organic layer includes a composition for an organic photoelectric device including a first compound for an organic photoelectric device represented by a combination of chemical formula 1 and chemical formula 2 and a second compound for an organic photoelectric device represented by chemical formula 3; and a dopant having a maximum emission wavelength of 570 to 750 nm.

In the chemical formulas 1 to 3,

x is O or S, and X is O or S,

t is a substituted or unsubstituted C6-C18 aryl, substituted or unsubstituted dibenzofuranyl, or substituted or unsubstituted dibenzothiophenyl,

ar is a substituted or unsubstituted C6 to C30 aryl group,

L、Y ¹and Y ²Independently a single bond, or a substituted or unsubstituted C6 to C20 arylene, adjacent two of formula 1 are linked to formula 2,

in chemical formula 1, not linked to ^ of chemical formula 2Independently is CR ^a，

R ^aAnd R ¹To R ¹²Independently hydrogen, deuterium, cyano, substituted or unsubstituted C1 to C20 alkyl, or substituted or unsubstituted C6 to C18 aryl,

R ¹³to R ²²Independently hydrogen, deuterium, cyano, amino, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C6 to C18 aryl, or substituted or unsubstituted carbazolyl,

R ¹³to R ²²Independently present or adjacent groups thereof are linked to each other to form a substituted or unsubstituted aromatic ring or a substituted or unsubstituted heteroaromatic ring, and

when R is ¹³To R ²²Independently of each other, R ¹³To R ²²Is a substituted or unsubstituted C6 to C18 aryl group or a substituted or unsubstituted carbazolyl group.

According to another embodiment, a display device including an organic optoelectronic device is provided.

[ advantageous effects ]

An organic photoelectric device having high efficiency and long life can be realized.

Drawings

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

< description of symbols >

100. 200: organic light emitting diode

105: organic layer

110: cathode electrode

120: anode

130: luminescent layer

140: hole assist layer

Detailed Description

[ best mode ]

Hereinafter, embodiments of the present invention are described in detail. However, these embodiments are exemplary, the present invention is not limited thereto, and the present invention is defined by the scope of the claims.

In the present specification, when a definition is not otherwise provided, "substituted" means that at least one hydrogen of a substituent or a compound is substituted with deuterium, halogen, hydroxyl, amino, substituted or unsubstituted C1 to C30 amine, nitro, substituted or unsubstituted C1 to C40 silyl, C1 to C30 alkyl, C1 to C10 alkylsilyl, C6 to C30 arylsilyl, C3 to C30 cycloalkyl, C3 to C30 heterocycloalkyl, C6 to C30 aryl, C2 to C30 heteroaryl, C1 to C20 alkoxy, C1 to C10 trifluoroalkyl, cyano, or a combination thereof.

In one example of the invention, "substituted" means that at least one hydrogen in the substituent or compound is substituted with deuterium, cyano, C1 to C30 alkyl, C1 to C10 alkylsilyl, C6 to C30 arylsilyl, C3 to C30 cycloalkyl, C3 to C30 heterocycloalkyl, C6 to C30 aryl, or C2 to C30 heteroaryl. Further, in particular embodiments of the invention, "substituted" means that at least one hydrogen in the substituent or compound is substituted with deuterium, cyano, C1 to C20 alkyl, C6 to C30 aryl, or C2 to C30 heteroaryl. Further, in particular embodiments of the invention, "substituted" means that at least one hydrogen in the substituent or compound is substituted with deuterium, cyano, C1 to C5 alkyl, C6 to C18 aryl, dibenzofuranyl, or dibenzothiophenyl. Further, in particular embodiments of the invention, "substituted" means that at least one hydrogen in the substituent or compound is substituted with deuterium, cyano, C1 to C5 alkyl, C6 to C18 aryl, dibenzofuranyl, or dibenzothiophenyl. Further, in particular embodiments of the present invention, "substituted" means that at least one hydrogen in the substituent or compound is substituted with deuterium, cyano, methyl, ethyl, propyl, butyl, phenyl, biphenyl, terphenyl, naphthyl, triphenyl, fluorenyl, dibenzofuranyl, or dibenzothiophenyl.

In the present specification, when a definition is not otherwise provided, "hetero" refers to a group containing one to three heteroatoms selected from N, O, S, P and Si in one functional group and the remainder being carbon.

In the present specification, when a definition is not otherwise provided, "alkyl" refers to an aliphatic hydrocarbon group. An alkyl group may be a "saturated alkyl group" without any double or triple bonds.

The alkyl group may be a C1 to C30 alkyl group. More specifically, the alkyl group may be a C1 to C20 alkyl group or a C1 to C10 alkyl group. For example, C1 to C4 alkyl groups may have 1 to 4 carbon atoms in the alkyl chain and may be selected from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl.

Specific examples of the alkyl group may be methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like.

In this specification, "aryl" refers to a group comprising at least one hydrocarbon aromatic moiety, and

all elements of the hydrocarbon aromatic moiety have p-orbitals that form conjugates, such as phenyl, naphthyl, and the like.

Two or more hydrocarbon aromatic moieties may be joined by sigma bonds, and may be, for example, biphenyl, terphenyl, quaterphenyl, or the like, or

Two or more hydrocarbon aromatic moieties are fused directly or indirectly to provide a non-aromatic fused ring. For example, it may be fluorenyl.

Aryl groups can include monocyclic, polycyclic, or fused-ring polycyclic (i.e., rings that share adjacent pairs of carbon atoms) functional groups.

In the present specification, "heterocyclic group" is a general concept of heteroaryl group, and may include at least one heteroatom selected from N, O, S, P and Si instead of carbon (C) in a cyclic compound, such as aryl group, cycloalkyl group, condensed ring thereof, or a combination thereof. When the heterocyclic group is a fused ring, the entire ring or each ring of the heterocyclic group may include one or more heteroatoms.

For example, "heteroaryl" may refer to an aryl group that includes at least one heteroatom selected from N, O, S, P and Si. Two or more heteroaryl groups are directly linked by a sigma bond, or when a heteroaryl group comprises two or more rings, the two or more rings may be fused. When the heteroaryl group is a fused ring, each ring may contain one to three heteroatoms.

Specific examples of the heterocyclic group may be pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, quinolyl, isoquinolyl, quinazolinyl and the like.

More specifically, the substituted or unsubstituted C6 to C30 aryl group and/or the substituted or unsubstituted C2 to C30 heterocyclic group may be a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthryl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted naphthonaphthyl group, a substituted or unsubstituted pyrenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted p-terphenyl group, a substituted or unsubstituted m-terphenyl group, a substituted or unsubstituted o-terphenyl group

A group, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted perylene group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted indenyl group, a substituted or unsubstituted furyl group, a substituted or unsubstituted thienyl 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 oxazolyl 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 pyrimidyl group, a substituted or unsubstituted pyrazinyl group, a substituted or unsubstituted triazinyl group, a substituted or unsubstituted benzofuranyl group, a substituted or unsubstituted benzothienyl group, a substituted or unsubstituted benzimidazolyl group, a substituted or unsubstituted benzofuranyl group, a substituted or unsubstituted pyruvenyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted pyrenyl group, a substituted or, Substituted or unsubstituted indolyl, substituted or unsubstituted quinolyl, substituted or unsubstituted isoquinolyl, substituted or unsubstituted quinazolinyl, substituted or unsubstituted quinoxalinyl, substituted or unsubstituted benzoquinolyl, substituted or unsubstituted benzoisoquinolyl, substituted or unsubstituted benzoquinazolinyl, substituted or unsubstituted naphthyridinyl, substituted or unsubstituted benzoxazinyl, substituted or unsubstituted benzothiazinyl, substituted or unsubstituted acridinyl, substituted or unsubstituted phenazinyl, substituted or unsubstituted naphthyridinyl, substituted or unsubstituted quinoxalinyl, substituted or unsubstituted quinolyl, quinolylA substituted or unsubstituted phenothiazinyl group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted dibenzothiophenyl group, or a combination thereof, but is not limited thereto.

In this specification, the hole characteristics refer to the ability to provide electrons to form holes when an electric field is applied, and the holes formed in the anode may be easily injected into the light emitting layer and transported in the light emitting layer due to the conductive characteristics according to the Highest Occupied Molecular Orbital (HOMO) level.

In addition, the electronic characteristic refers to an ability to accept electrons when an electric field is applied, and electrons formed in the cathode may be easily injected into the light emitting layer and transported in the light emitting layer due to a conductive characteristic according to a Lowest Unoccupied Molecular Orbital (LUMO) level.

Hereinafter, an organic light emitting diode, which is one example of an organic photoelectric device according to an embodiment, is described with reference to the accompanying drawings.

Fig. 1 and 2 are cross-sectional views of respective organic light emitting diodes according to an embodiment.

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

The organic layer according to an embodiment of the present invention includes a composition for an organic photoelectric device, the composition including a first compound for an organic photoelectric device represented by a combination of chemical formula 1 and chemical formula 2 and a second compound for an organic photoelectric device represented by chemical formula 3; and a dopant having a maximum emission wavelength of 600nm to 650 nm.

In the chemical formulas 1 to 3,

x is O or S, and X is O or S,

t is a substituted or unsubstituted C6-C18 aryl, substituted or unsubstituted dibenzofuranyl, or substituted or unsubstituted dibenzothiophenyl,

ar is a substituted or unsubstituted C6 to C30 aryl group,

L、Y ¹and Y ²Independently a single bond, or a substituted or unsubstituted C6 to C20 arylene, adjacent two of formula 1 are linked to formula 2,

in chemical formula 1, not linked to chemical formula 2 is independently CR ^a，

For example, R ^aAnd R ¹To R ¹²Independently hydrogen, deuterium, cyano, substituted or unsubstituted C1 to C20 alkyl, or substituted or unsubstituted C6 to C18 aryl,

R ¹³to R ²²Independently hydrogen, deuterium, cyano, amino, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C6 to C18 aryl, or substituted or unsubstituted carbazolyl,

R ¹³to R ²²Independently present or adjacent groups thereof are linked to each other to form a substituted or unsubstituted aromatic ring or a substituted or unsubstituted heteroaromatic ring,

when R is ¹³To R ²²Independently of each other, R ¹³To R ²²Is a substituted or unsubstituted C6 to C18 aryl group, or a substituted or unsubstituted carbazolyl group.

In particular, the second compound for an organic photoelectric device is preferably one showing a current density of 1500mA/cm measured at a voltage of 7V in a subsequent HOD (hole only device) device ²To 2500mA/cm ²The compound of (1).

HOD device: ITO/Compound C

Second Compound for organic optoelectronic device of the present invention /Al

Compound C: n- (biphenyl-4-yl) -9, 9-dimethyl-N- (4- (9-phenyl-9H-carbazol-3-yl) phenyl) -9H-fluoren-2-amine

The organic optoelectronic devices of the present invention comprise phosphorescent dopants having a maximum emission wavelength of from 570nm to 750 nm. That is, it includes a phosphorescent dopant having a maximum emission wavelength outside the green region. For example, the maximum emission wavelength may be 570nm to 750nm, which is a wavelength of a reddish region, and may be 570nm to 720nm, 580nm to 700nm, 590nm to 700nm, or 600nm to 650 nm.

When the maximum emission wavelength of a mixture of the first compound for an organic photoelectric device and the second compound for an organic photoelectric device is 450nm to 550nm, the long-life characteristic of the organic photoelectric device emitting light in a red region, as in the present invention, and a phosphorescent dopant having a maximum emission wavelength of 570nm to 750nm may be surely included. In order for the maximum emission wavelength of the mixture of the first compound for the organic photoelectric device and the second compound for the organic photoelectric device to be 450nm to 550nm, the difference between the LUMO level of the first compound for the organic photoelectric device and the HOMO level of the second compound for the first compound for the organic photoelectric device should be 2.30eV to 3.00 eV.

On the other hand, in the present specification, the HOD is an organic light emitting diode manufactured to include two organic thin layers, and the specific structure is as follows.

ITO/Compound C

Second compound for organic photoelectric device

/Al

Compound C: n- (biphenyl-4-yl) -9, 9-dimethyl-N- (4- (9-phenyl-9H-carbazol-3-yl) phenyl) -9H-fluoren-2-amine

In the device configured as an HOD in the present specification, a current density measured at a voltage of 7V was obtained as a calculated value by measuring a current flowing through a cell device using a current-voltage meter (Keithley2400), while increasing the voltage from-6V to 8V with respect to an organic light emitting diode including a second compound for an organic photoelectric device in one organic thin layer as described above, and then dividing the current at 7V by an area.

In HOD devices, the current density measured at a voltage of 7V may be specifically 2000mA/cm ²To 2500mA/cm ²And more specifically 2000mA/cm ²To 2300mA/cm ²。

In other words, when the HOD device has a current density, since the second compound for an organic photoelectric device according to the present invention improves hole transport ability in the red phosphorescent device together with the first compound for an organic photoelectric device as a host, the HOD device may exhibit excellent lifetime and luminous efficiency.

In an exemplary embodiment of the present invention, a first compound for an organic photoelectric device included in a composition for an organic photoelectric device may have a LUMO level in a range of-3.0 eV to-3.3 eV, and a second compound for an organic photoelectric device may have a HOMO level in a range of-5.5 eV to-6.0 eV. Here, as described above, the maximum emission wavelength of the mixture of the first compound for an organic photoelectric device and the second compound for an organic photoelectric device may be 450nm to 550 nm. Further, a difference between HOMO levels of the first compound for an organic photoelectric device and the second compound for an organic photoelectric device may be 0.2eV to 0.5 eV.

In certain exemplary embodiments of the present invention, the difference between the HOMO levels of the first compound for an organic opto-electronic device and the second compound for an organic opto-electronic device may be 0.2eV to 0.4eV, and preferably 0.2eV to 0.3 eV.

The energy level was calculated by using as a reference the value measured by an electrochemical analyzer (epsilon ec & C3 cell stand, windtech), where a working electrode was formed by dispersing the measurement material in a solvent and then dropping the solution into a carbon electrode to form a film, Ag/AgCl was used as a reference electrode, and Pt was used as a counter electrode. An electrolyte solution was prepared by using 0.1M tetrabutylammonium perchlorate, and the energy level of the measurement material was calculated by using the measurement value of ferrocene of-4.8V as a reference.

In an exemplary embodiment of the present invention, the first compound for an organic photoelectric device may be represented by one of chemical formula 1A, chemical formula 1B, chemical formula 1C, chemical formula 1D, chemical formula 1E, and chemical formula 1F.

In chemical formula 1A, chemical formula 1B, chemical formula 1C, chemical formula 1D, chemical formula 1E and chemical formula 1F, X, T, Ar, L, Y ¹、Y ²And R ¹To R ⁷Is the same as above, and R ^a1To R ^a4And R ¹To R ⁷The same is true.

In one embodiment of the present invention, "substituted" of chemical formulas 1 and 2 means that at least one hydrogen of the substituent or compound is substituted with deuterium, cyano, phenyl, biphenyl, or naphthyl.

In certain example embodiments of the present invention, the first compound for an organic photoelectric device may be represented by chemical formula 1B or chemical formula 1C, for example, chemical formula 1B may be represented by one of chemical formula 1B-1 to chemical formula 1B-4, and chemical formula 1C may be represented by one of chemical formula 1C-1 to chemical formula 1C-4.

In chemical formulas 1B-1 to 1B-4 and 1C-1 to 1C-4, X, T, Ar, L, Y ¹、Y ²And R ¹To R ⁷As described above.

The first compound for an organic photoelectric device may preferably be represented by one of chemical formula 1B-2, chemical formula 1B-3, chemical formula 1C-2, and chemical formula 1C-3, and may more preferably be represented by one of chemical formula 1B-2 or chemical formula 1C-2.

T of chemical formula 1 may be specifically a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted dibenzothiophenyl group, and is preferably a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, or a substituted or unsubstituted terphenyl group, and may be selected, for example, from group I substituents.

[ group I ]

T of chemical formula 1 may be more preferably phenyl.

Ar of chemical formula 2 may preferably be a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, or a substituted or unsubstituted terphenyl group, for example, a substituent of group I.

Ar of chemical formula 2 may be more preferably phenyl.

L, Y of chemical formula 1 ¹And Y ²May be a single bond, a substituted or unsubstituted phenylene group, or a substituted or unsubstituted biphenylene group, and may be, for example, a single bond or a linking group selected from group II.

[ group II ]

L, Y of chemical formula 1 ¹And Y ²May more preferably be a single bond.

R of chemical formula 1 and chemical formula 2 ¹To R ⁷May preferably be hydrogen or phenyl, and R ¹、R ²、R ⁶And R ⁷May more preferably be all hydrogen, and R ³And R ⁴It may be hydrogen or phenyl.

In exemplary embodiments of the present invention, the second compound for an organic photoelectric device may be represented by chemical formula 3, and may be represented by R according to chemical formula 3 ¹³To R ²²Is represented by one of chemical formula 3A-1, chemical formula 3A-2, chemical formula 3B-1, chemical formula 3B-2, chemical formula 3B-3, chemical formula 3B-4 and chemical formula 3B-5.

In one embodiment of the present invention, "substituted" of chemical formula 3 means that at least one hydrogen of the substituent or compound is substituted with deuterium, cyano, phenyl, biphenyl, or naphthyl.

Specifically, when R of chemical formula 3 ¹³To R ²²Each independently of the other, R ¹³To R ²²May be a substituted or unsubstituted C6 to C18 aryl group, or a substituted or unsubstituted carbazolyl group, and may be represented, for example, by chemical formula 3A-1 or chemical formula 3A-2 according to the substitution direction of the substituted or unsubstituted C6 to C18 aryl group and the substituted or unsubstituted carbazolyl group.

In chemical formulas 3A-1 and 3A-2, R ⁸To R ¹⁷Independently hydrogen, deuterium, cyano, amino, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C6 to C18 aryl, or substituted or unsubstituted carbazolyl, R ¹³To R ¹⁷Independently present or adjacent groups thereof are linked to each other to form a substituted or unsubstituted aromatic or substituted or unsubstituted aromatic heteroaromatic ring, and R ¹⁹To R ²¹Is a substituted or unsubstituted C6 to C18 aryl group, or a substituted or unsubstituted carbazolyl group.

R of chemical formula 3A-1 and chemical formula 3A-2 ⁸To R ¹²May be hydrogen or phenyl, and more preferably is all hydrogen.

Further, R of chemical formula 3A-1 and chemical formula 3A-2 ¹³To R ¹⁷May independently be hydrogen, substituted or unsubstituted phenyl or substituted or unsubstituted biphenyl, and R ¹³To R ¹⁷Are linked to each other to form a substituted or unsubstituted naphthyl group, wherein the substituents may be phenyl, biphenyl, or naphthyl groups. Further, in an exemplary embodiment of the invention, R ¹³To R ¹⁷Are each hydrogen, R ¹⁴To R ¹⁶Can be phenyl or biphenyl, and in another exemplary embodiment, R ¹³To R ¹⁷Are both hydrogen or R ¹³、R ¹⁴、R ¹⁶And R ¹⁷May all be hydrogen, and R ¹⁵May be phenyl.

Further, R in chemical formula 3A-1 and chemical formula 3A-2 ¹⁹To R ²¹May be a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted terphenyl group, or a substituted or unsubstituted carbazolyl group, and may be, for example, a substituent selected from group III.

[ group III ]

In exemplary embodiments of the present invention, R of chemical formula 3A-1 and chemical formula 3A-2 ¹⁹To R ²¹At least one of which may be phenyl or carbazolyl, and R ²⁰May be phenyl or carbazolyl.

Meanwhile, when R of chemical formula 3 ¹³To R ¹⁷Or R ¹⁸To R ²²When adjacent groups of (a) are linked to form a substituted or unsubstituted aromatic ring or a substituted or unsubstituted heteroaromatic ring, R is included ¹³To R ¹⁷Or R ¹⁸To R ²²The benzene ring of (A) may form a substituted or unsubstitutedA naphthyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted triphenylene group, or a substituted or unsubstituted carbazolyl group, and may be represented by, for example, one of chemical formula 3B-1, chemical formula 3B-2, chemical formula 3B-3, chemical formula 3B-4, and chemical formula 3B-5.

In chemical formula 3B-1, chemical formula 3B-2, chemical formula 3B-3, chemical formula 3B-4 and chemical formula 3B-5, R ⁸To R ¹⁷Same as above, R ^b、R ^c、R ^dAnd R ^eIndependently is hydrogen, deuterium, cyano, substituted or unsubstituted C1 to C20 alkyl, or substituted or unsubstituted C6 to C18 aryl, and Ar ^aIs a substituted or unsubstituted C6 to C18 aryl group.

R of chemical formula 3B-1, chemical formula 3B-2, chemical formula 3B-3, chemical formula 3B-4 and chemical formula 3B-5 ¹³To R ¹⁷May independently be hydrogen, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, or substituted or unsubstituted naphthyl or adjacent groups thereof may be linked to each other to form a substituted or unsubstituted naphthyl. Herein, "substituted" means substituted with phenyl, biphenyl, or naphthyl.

In certain example embodiments of the present invention, the second compound for an organic photoelectric device may be represented by chemical formula 3A, and preferably, chemical formula 3A-1.

Here, R of chemical formula 3A-1 ²⁰May be a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted phenanthrenyl group, a substituted or unsubstituted triphenylenyl group, or a substituted or unsubstituted carbazolyl group, and in more specific exemplary embodiments, may be a phenyl group or a carbazolyl group.

The composition for an organic photoelectric device according to more specific example embodiments of the present invention may include a first compound for an organic photoelectric device represented by chemical formula 1B-2 or chemical formula 1C-2 and a second compound for an organic photoelectric device represented by chemical formula 3A-1. Here, X of chemical formula 1B-2 and chemical formula 1C-2 may be O or S, T may be substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted terphenyl, substituted or unsubstituted dibenzofuranyl, or substituted or unsubstituted dibenzothiophenyl, Ar is substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, or substituted or unsubstituted terphenyl, L, Y ¹And Y ²May independently be a single bond, a substituted or unsubstituted phenylene group or a substituted or unsubstituted biphenylene group, R ¹To R ⁷And may be independently hydrogen, substituted or unsubstituted C1 to C5 alkyl, or substituted or unsubstituted phenyl, R of formula 3A-1 ⁸To R ¹²May be hydrogen, or substituted or unsubstituted phenyl, R ¹³To R ¹⁷May independently be hydrogen, substituted or unsubstituted phenyl, or substituted or unsubstituted biphenyl, R ¹³To R ¹⁷May be linked to each other to form a substituted or unsubstituted naphthyl group, and R ²⁰May be a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted terphenyl group, or a substituted or unsubstituted carbazolyl group.

The compound for an organic photoelectric device represented by the combination of chemical formula 1 and chemical formula 2 may be, for example, selected from the group 1 compounds, and the compound for an organic photoelectric device represented by chemical formula 3 may be, for example, selected from the group 2 compounds, but is not limited thereto.

[ group 1]

[ group 2]

The aforementioned organic layer (105) includes a light-emitting layer (130), and may include a composition for an organic photoelectric device as a host, for example, a red host of the light-emitting layer.

The anode (120) may be made of a conductor with a large work function to aid hole injection, and may be made of, for example, a metal oxide, and/or a conductive polymer. The anode (120) may be, for example, a metal such as nickel, platinum, vanadium, chromium, copper, zinc, gold, or the like, or an alloy thereof; metal oxides such as zinc oxide, Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), and the like; combinations of metals and oxides, e.g. ZnO and Al or SnO ₂And Sb; conductive polymers such as poly (3-methylthiophene), poly (3,4- (ethylene-1, 2-dioxy) thiophene) (PEDT), polypyrrole and polyaniline, but are not limited thereto.

The cathode (110) may be made of a conductor having a small work function to aid electron injection, and may be made of, for example, a metal oxide, and/or a conductive polymer. The cathode (110) may be, for example, a metal or alloy thereof, such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum silver, tin, lead, cesium, barium, and the like; multilayer materials such as LiF/Al, LiO ₂Al, LiF/Ca, LiF/Al and BaF ₂But not limited thereto,/Ca.

Fig. 2 is a sectional view illustrating an organic light emitting diode according to another embodiment.

Referring to fig. 2, the organic light emitting diode (200) includes a hole assist layer (140) in addition to the light emitting layer (130). The hole assist layer (140) may further increase hole injection and/or hole mobility and block electrons between the anode (120) and the light emitting layer (130). 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 organic layer (105) of fig. 1 or 2 may further include an electron injection layer, an electron transport auxiliary layer, a hole transport auxiliary layer, a hole injection layer, or a combination thereof, even though they are not shown. These organic layers may contain compounds useful in the organic opto-electronic devices of the present invention. The organic light emitting diodes (100) and (200) may be manufactured by forming an anode or a cathode on a substrate, forming an organic layer using a dry film forming method such as a vacuum deposition method (evaporation), sputtering, plasma plating, and ion plating, or a wet coating method such as spin coating, dip coating, and flow coating, and forming the cathode or the anode thereon.

The above-described first compound for an organic photoelectric device and the second compound for an organic photoelectric device may be differently provided in various compositions, and the mobility of charges may be controlled by controlling the ratio of the compounds. When the composition of the present invention is used as a host, the combination ratio thereof may be different depending on the type and properties of a dopant used, and the first compound for an organic photoelectric device and the second compound for an organic photoelectric device may be, for example, 1: 10 to 10: a weight ratio of 1 is included. Specifically, they may be present in a ratio of 2: 8 to 8: 2. 2: 8 to 7: 3. 2: 8 to 6: 4. 2: 8 to 5: 5. 3:7 to 8: 2. 3:7 to 7: 3. 3:7 to 6: 4, e.g. 3:7 to 5: a weight ratio of 5 is included. For a more specific example, the mixing ratio of the first compound for an organic photoelectric device and the second compound for an organic photoelectric device may be 3: 7. 4: 6 or 5: 5.

the composition may further comprise one or more host compounds in addition to the first compound for an organic opto-electronic device and the second compound for an organic opto-electronic device.

The dopant may be a red phosphorescent dopant.

The dopant is mixed in a small amount to cause light emission, and may be generally a material such as a metal complex which emits light by being excited to a triplet state or a multiple state multiple times. The dopant may be, for example, an inorganic, organic or organic/inorganic compound, and one or more of them may be used.

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

[ chemical formula Z ]

L ₂MX

In formula Z, M is a metal, and L and X are the same or different and are ligands that form complex compounds with M.

M may be, for example, Ir, Pt, Os, Ti, Zr, Hf, Eu, Tb, Tm, Fe, Co, Ni, Ru, Rh, Pd, or combinations thereof, and L and X may be, for example, bidentate ligands.

The organic optoelectronic devices of the present invention comprise phosphorescent dopants having a maximum emission wavelength of from 570nm to 750 nm. That is, it includes a phosphorescent dopant having a maximum emission wavelength outside the green region. For example, the maximum emission wavelength may be 570nm to 720nm, 580nm to 700nm, 590nm to 700nm, 600nm to 700nm, or 600nm to 650nm, which is the wavelength of the red region.

The phosphorescent dopant having a maximum emission wavelength of 570nm to 750nm according to the present invention may be an iridium (Ir) complex or a platinum (Pt) complex, and the platinum (Pt) complex may be represented by, for example, chemical formula 4-1. In addition, the iridium (Ir) complex may be represented by, for example, chemical formula 4-2.

[ chemical formula 4-1]

In the chemical formula 4-1,

X ^A、X ^B、X ^Cand X ^DIs an element forming an unsaturated ring with each of 1A, 1B, 1C and 1D and independently C or N.

1A, 1B, 1C and 1D are independently substituted or unsubstituted C6 to C30 aryl, or substituted or unsubstituted C2 to C30 heterocyclyl,

L ^A、L ^B、L ^C、L ^D、Q ^A、Q ^B、Q ^Cand Q ^DIndependently a single bond, O, S, a substituted or unsubstituted C1 to C30 alkylene, a substituted or unsubstituted C2 to C30 alkenylene, a substituted or unsubstituted C6 to C30 arylene, or a substituted or unsubstituted C2 to C30 heteroarylene,

R ^A、R ^B、R ^Cand R ^DIndependently hydrogen, deuterium, cyano, halogen, silyl, phosphino, amine, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, or substituted or unsubstituted C2 to C30 heteroaryl,

R ^A、R ^B、R ^Cand R ^DIndependently present or adjacent groups thereof being linked to each otherSo as to form a ring,

n is one of integers from 0 to 5, and

a. b, c and d are independently one of integers from 0 to 3.

[ chemical formula 4-2]

In the chemical formula 4-2,

2A, 2B and 2C are independently substituted or unsubstituted benzene rings,

at least one of 2A, 2B and 2C forms a condensed ring with an adjacent complex compound,

R ^E、R ^F、R ^G、R ^H、R ^I、R ^Jand R ^KIndependently hydrogen, deuterium, cyano, halogen, silyl, phosphino, amine, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C6 to C30 aryl, or substituted or unsubstituted C2 to C30 heteroaryl,

R ^E、R ^F、R ^G、R ^H、R ^I、R ^Jand R ^KIndependently present or adjacent groups thereof are linked to each other to form a ring, and

m is one of integers of 1 to 3.

In exemplary embodiments of the present invention, the platinum (Pt) complex may be represented by chemical formula 4-1a or chemical formula 4-1 b.

In chemical formulas 4-1a and 4-1b, X ^A、X ^B、X ^C、X ^D、1A、1B、1C、1D、L ^A、L ^B、L ^C、L ^D、Q ^A、Q ^B、Q ^C、Q ^D、R ^A、R ^B、R ^C、R ^DA, b, c and d are as defined above.

In certain exemplary embodiments of the invention, 1A, 1B, 1C, and 1D can independently be a substituted or unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted C2 to C20 heterocyclic group, more specifically, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted phenanthrenyl group, a substituted or unsubstituted triphenylenyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted benzimidazolyl group, a substituted or unsubstituted benzothiazolyl group, a substituted or unsubstituted benzoxazolyl group, a substituted or unsubstituted pyrrolyl group, a substituted or unsubstituted pyrazolyl group, a substituted or unsubstituted imidazolyl group, a substituted or unsubstituted oxazolyl group, and may for example be selected from group IV, and groups of group IV may be further substituted.

[ IV group ]

In group IV, X is an element forming an unsaturated ring with each of 1A, 1B, 1C, and 1D, and is independently C or N. Additional substituents may be deuterium, cyano, halogen, C1 to C10 alkyl or C1-C10 fluoroalkyl.

More preferably, 1A, 1B, 1C and 1D may be substituted or unsubstituted phenyl, substituted or unsubstituted pyridyl, substituted or unsubstituted benzimidazolyl, substituted or unsubstituted benzothiazolyl, substituted or unsubstituted pyrrolyl or substituted or unsubstituted pyrazolyl.

In certain exemplary embodiments of the invention, when a, b, c and d are 2 or greater, the substituent R ^A、R ^B、R ^CAnd R ^DEach of which may be the same or different.

Meanwhile, specific examples of the present invention include wherein R ^A、R ^B、R ^CAnd R ^DAdjacent groups of (a) are fused to form a ring structure. For example, group 3 can be instantiatedCompound 3-5 or compound 3-8.

In exemplary embodiments of the present invention, the iridium (Ir) complex may be represented by chemical formula 4-2a or chemical formula 4-2 b.

In chemical formulas 4-2a and 4-2b, R ^E、R ^F、R ^G、R ^H、R ^I、R ^J、R ^KAnd m is as defined above, and R ^L、R ^MAnd R ^NDefinition of (A) and R ^E、R ^F、R ^G、R ^H、R ^I、R ^JAnd R ^KThe same definition is applied.

In certain exemplary embodiments of the invention, R ^E、R ^F、R ^G、R ^H、R ^I、R ^J、R ^K、R ^L、R ^MAnd R ^NMay be hydrogen, deuterium, cyano, halogen, C1 to C10 alkyl, or C1 to C10 fluoroalkyl.

Meanwhile, specific examples of the present invention include wherein R ^E、R ^F、R ^GAnd R ^HAdjacent groups of (a) are fused to form a ring structure. For example, compounds 4 to 12 of group 3 can be exemplified.

The phosphorescent dopant may be, for example, selected from group 3 compounds, but is not limited thereto.

[ group 3]

In the most specific exemplary embodiment of the present invention, the phosphorescent dopant may be represented by chemical formula 4-2 a.

More specifically, the phosphorescent dopant may be included in an amount of 0.1 to 50 wt% based on 100 wt% of the composition of the first compound for an organic photoelectric device and the second compound for an organic photoelectric device. The phosphorescent dopant may be included in an amount of 0.1 to 20 wt% based on 100 wt% of a composition of the first compound for an organic photoelectric device and the second compound for an organic photoelectric device. Most specifically, the phosphorescent dopant may be included in an amount of 0.5 to 10 wt% based on 100 wt% of the composition of the first compound for an organic photoelectric device and the second compound for an organic photoelectric device.

The composition may be formed by using a dry deposition method or a solution method such as Chemical Vapor Deposition (CVD).

The organic light emitting diode can be applied to an organic light emitting diode display.

[ modes for the invention ]

Hereinafter, embodiments are explained in more detail with reference to examples however, these examples should not be construed as limiting the scope of the present invention in any sense.

Hereinafter, starting materials and reactants used in examples and synthesis examples were purchased from Sigma-aldrich co.ltd. or TCI inc.

(preparation of Compound for organic photoelectric device)

A compound as one specific example of the present invention was synthesized by the following procedure.

(first Compound for organic photoelectric device)

Synthesis example 1: synthesis of Compound A-1

[ reaction scheme 1]

The first step is as follows: synthesis of 4-bromo-2-fluoro-1- (2-methoxyphenyl) benzene

2-Methoxyphenylboronic acid (50.0g,329mmol), 4-bromo-2-fluoro-1-iodobenzene (99.0g,329mmol), tetrakis (triphenylphosphine) palladium (0) (19.0g,16mmol) and potassium carbonate (113.7g,823mmol) were dissolved in 2L of tetrahydrofuran: DIW 2: 1, then refluxed, and stirred at 80 ℃ for 12 hours. Upon completion of the reaction, the residue was purified by column chromatography using a mixed solution of dichloromethane: n-hexane to obtain 4-bromo-2-fluoro-1- (2-methoxyphenyl) benzene (78.0g, Y ═ 84.3%) by extracting the organic layer, evaporating all the solvent and then purifying the residue.

The second step is that: synthesis of 4-bromo-2-fluoro-1- (2-hydroxyphenyl) benzene

4-bromo-2-fluoro-1- (2-methoxyphenyl) benzene (78.0g,277mmol) was dissolved in 500mL of dichloromethane, to which 694mL of a 1M boron tribromide solution was then added dropwise at 0 ℃. The mixture was stirred at room temperature under a stream of nitrogen. When the reaction was completed, the solution was dropped into water, and extracted twice with ethyl acetate. The organic layer was purified by column chromatography using a mixed solution of n-hexane and dichloromethane to obtain 4-bromo-2-fluoro-1- (2-hydroxyphenyl) benzene (70.2g, Y ═ 94.7%).

The third step: synthesis of 3-bromodibenzofuran

4-bromo-2-fluoro-1- (2-hydroxyphenyl) benzene (70.0g,262mmol) and potassium carbonate (72.5g,524mmol) were dissolved in 800mL of N-methyl-2-pyrrolidone, followed by stirring under a nitrogen stream at 130 ℃ for 3 hours. When the reaction was complete, the solvent was evaporated all over and then extracted once with dichloromethane and water. After removal of dichloromethane, the slurry obtained therefrom was purified with methanol to obtain 3-bromodibenzofuran (57.4g, Y ═ 88.6%).

The fourth step: synthesis of 2-chloro-4-dibenzofuran-3-yl-6-phenyl-1, 3, 5-triazine

2-chloro-4-dibenzofuran-3-yl-6-phenyl-1, 3, 5-triazine (Y ═ 48.3%) was synthesized according to the same method as the first step by using 2, 4-dichloro-6-phenyl-1, 3, 5-triazine and 3-bromodibenzofuran as starting materials.

The fifth step: 12-phenyl-11H-indolo [2,3-a ]]Synthesis of carbazole

Indolo [2,3-a ] carbazole (20.0g,78mmol), bromobenzene (12.3g,78mmol), copper (I) iodide (2.97g,16mmol), potassium carbonate (16.2g,117mmol) and 1, 10-phenanthroline (2.8g,16mmol) were placed in 260mL of N, N-dimethylformamide, then refluxed and stirred under a nitrogen stream for 12 hours. When the reaction was complete, after complete evaporation of the solvent, the residue was dissolved in toluene and filtered through silica gel. The filtered solution was recrystallized to obtain 12-phenyl-11H-indolo [2,3-a ] carbazole (19.6g, Y ═ 76%).

And a sixth step: synthesis of Compound A-1

12-phenyl-11H-indolo [2,3-a ] carbazole (10.0g,28mmol) and 2-chloro-4-dibenzofuran-3-yl-6-phenyl-1, 3, 5-triazine (18.6g,56mmol) were placed in 100mL of N, N-dimethylformamide and then cooled to 0 ℃. After 10 minutes, sodium hydride (1.34g,56mmol) was added thereto, followed by stirring at room temperature under a nitrogen stream for 12 hours. When the reaction was complete, after complete evaporation of the solvent, the residue was dissolved in chlorobenzene and then filtered through silica gel. The filtered solution was recrystallized to obtain compound a-1(16.5g, Y ═ 90%).

Synthesis example 2: synthesis of Compound A-74

[ reaction scheme 2]

The first step is as follows: synthesis of 4-bromo-9-phenyl-carbazole

Synthesis was performed according to the same method as the fifth step of synthesis example 1 using 4-bromo-9H-carbazole as a starting material, and column chromatography purification was performed using a mixed solution of n-hexane and dichloromethane. (Y72%)

The second step is that: synthesis of 9-phenyl-4- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane-2-yl) carbazole

4-bromo-9-phenyl-carbazole (30.0g,93mmol), bis (pinacol) diboron (35.5g,140mmol), potassium acetate (27.4g,279mmol) and [1, 1' -bis (diphenylphosphino) ferrocene ] -dichloropalladium (II) (3.0g,4mmol) were added to 450mL of N, N-dimethylformamide, then refluxed and stirred at 150 ℃ for 12 hours. When the reaction was complete, the solution was added to excess DIW to form a precipitate. The precipitate was filtered, then boiled and dissolved in toluene and filtered over silica gel.

After the solvent of the filtered solution was totally evaporated, the residue thereof was recrystallized with a mixed solution of dichloromethane: n-hexane to obtain 9-phenyl-4- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane-2-yl) carbazole (29.2g, Y ═ 84.9%).

The third step: synthesis of 4- (2-nitrophenyl) -9-phenylcarbazole

According to the same method as the first step of Synthesis example 1, synthesis was carried out using 9-phenyl-4- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane-2-yl) carbazole and 1-bromo-2-nitrobenzene as starting materials, and using a mixed solution of n-hexane: dichloromethane for recrystallization to obtain 4- (2-nitrophenyl) -9-phenylcarbazole. (Y82%)

The fourth step: 5-phenyl-5, 8-indolino [2,3-c ]]Synthesis of carbazole

4- (2-Nitrophenyl) -9-phenylcarbazole (20.0g,55mmol) and triphenylphosphine (28.8g,110mmol) were placed in 1, 2-dichlorobenzene and then stirred at 180 ℃ for 12 hours under a stream of nitrogen. When the reaction was completed, the solvent was completely evaporated, and a mixed solution of n-hexane: dichloromethane was used for column chromatography purification to obtain 5-phenyl-5, 8-indolino [2,3-c ] carbazole (11g, Y ═ 60.3%).

Calcd for C18H12N 2: c, 86.72; h, 4.85; n, 8.43; obtaining a value: c, 86.70; h, 4.83; n,8.47

The fifth step: synthesis of Compound A-74

According to the same method as the sixth step of Synthesis example 1, 5-phenyl-5, 8-indolino [2,3-c ] carbazole and 2-chloro-4-dibenzofuran-3-yl-6-phenyl-1, 3, 5-triazine were used as starting materials for synthesis to obtain Compound A-74. (Y70%)

(second Compound for organic photoelectric device)

Synthetic example 3: synthesis of Compound B-1

[ reaction scheme 3]

8g (31.2mmol) of intermediate I-1, 20.5g (73.32mmol) of 4-iodobiphenyl, 1.19g (6.24mmol) of CuI, 1.12g (6.24mmol) of 1, 10-phenanthroline and 12.9g (93.6mmol) of K ₂CO ₃Put into a round bottom flask, 50ml of DMF was added thereto, and the mixture was refluxed and stirred under nitrogen atmosphere for 24 hours. When the reaction was completed, distilled water was added thereto to perform precipitation, and the thus-obtained solid was filtered. The solid was dissolved in 250ml of xylene, filtered through silica gel, and precipitated to a white solid to obtain the target compound B-1(16.2g, Y ═ 93%).

Synthetic example 4: synthesis of Compound B-2

[ reaction scheme 4]

In a 500mL flask, 10.0g (30.2mmol) of 5-phenyl-5, 8-indolino [2,3-c ] synthesized in the fourth step of Synthesis example 2 was placed]Carbazole, 14.4g (36.2mmol) of 3- (4-bromophenyl) -9-phenyl-9H carbazole, 4.3g (45.3mmol) of sodium tert-butoxide (NaOtBu), 1.0g (1.8mmol) of Pd (dba) ₂And 2.2g (50% in toluene) of tri-tert-butylphosphine (P (tBu) ₃) Placed in 150mL of xylene, then heated and refluxed under a stream of nitrogen for 12 hours. After removing xylene, 200mL of methanol was added to the thus-obtained mixture, and the crystallized solid was filtered, dissolved in methylene chloride, filtered through silica gel/celite, and recrystallized from acetone after removing an appropriate amount of organic solvent to obtain Compound B-2(15.0g, yield 77%).

Calculated values: C47H30N 4S: c, 88.72; h, 4.81; n, 6.47; obtaining a value: c, 88.74; h, 4.82; n,6.44

Comparative synthesis example 1: synthesis of Compound ET1

Compound ET1 was synthesized with reference to the synthesis described in KR0955993B 1.

Comparative synthesis example 2: synthesis of Compound ET2

Compound ET2 was synthesized with reference to the synthesis described in KR1477613B 1.

Comparative synthesis example 3: synthesis of Compound HT1

Compound HT1 was synthesized with reference to the synthetic method described in JP3139321B 2.

Comparative synthesis example 4: synthesis of Compound HT2

Compound HT2 was synthesized with reference to the synthesis described in KR2011-068330 a.

Comparative synthesis example 5: synthesis of Compound HT3

Compound HT3 was synthesized with reference to the synthesis described in KR 2015-0003658A.

Comparative synthesis example 6: synthesis of Compound HT4

Compound HT4 was synthesized with reference to the synthesis described in KR 2015-0003658A.

Comparative synthesis example 7: synthesis of Compound HT5

Compound HT5 was synthesized with reference to the synthesis described in KR 2016-0126698A.

Comparative synthesis example 8: synthesis of Compound HT6

Compound HT6 was synthesized with reference to the synthesis described in KR1477613B 1.

Comparative synthesis example 9: synthesis of Compound HT7

Compound HT7 was synthesized with reference to the synthesis described in KR1477613B 1.

(production of organic light emitting diode)