CN113563357A - Compound for organic photoelectric device, composition for organic photoelectric device, and display device - Google Patents

Abstract

The present invention relates to a compound for an organic photoelectric device, a composition for an organic photoelectric device, and a display device. Specifically, disclosed are a compound for an organic photoelectric device represented by a combination of chemical formula 1 and chemical formula 2, and a composition for an organic photoelectric device, and a display device including the same. The details of chemical formula 1 and chemical formula 2 are as described in the specification.

Description

Compound for organic photoelectric device, composition for organic photoelectric device, and display device

Citations to related applications

This application claims priority and benefit to korean patent application No. 10-2020-0051731 filed in korean intellectual property office on 28.4.2020, which is incorporated herein by reference in its entirety.

Technical Field

Disclosed are a compound for an organic photoelectric device, a composition for an organic photoelectric device, and a display device.

Background

An organic photoelectric device (organic photodiode) is a device capable of converting electric energy and light energy into each other.

Organic photoelectric devices can be roughly classified into two types according to the operation principle. One is an optoelectronic device that generates electric energy by separating excitons formed by light energy into electrons and holes and transferring the electrons and holes to different electrodes, respectively, and the other is light emission that generates light energy from electric energy by supplying voltage or current to the electrodes.

Examples of the organic photoelectric device include an organic optoelectronic device, an organic light emitting diode, an organic solar cell, and an organic photosensitive drum.

Among them, Organic Light Emitting Diodes (OLEDs) have been receiving attention in recent years due to the increasing demand for flat panel display devices. The organic light emitting diode is a device that converts electric energy into light, and the performance of the organic light emitting diode is greatly affected by an organic material disposed between electrodes.

Disclosure of Invention

One embodiment provides a compound for an organic photoelectric device, which can realize an organic photoelectric device having high efficiency, long life, and low driving voltage.

Another embodiment provides a composition for an organic photoelectric device including the compound.

Another embodiment provides an organic photoelectric device including the compound or the composition.

Another embodiment provides a display device including an organic photoelectric device.

According to one embodiment, there is provided a compound represented by a combination of chemical formula 1 and chemical formula 2.

In chemical formula 1 and chemical formula 2,

ar is a substituted or unsubstituted C6 to C12 aryl group,

l is a single bond or a substituted or unsubstituted C6 to C20 arylene group,

X¹and X²Independently of each other is O or S,

a of chemical formula 1₁ ^*To a₄ ^*Independently is a linking carbon (C) or CR^a，

A of chemical formula 1₁ ^*To a₄ ^*Two adjacent of (a) are each linked to x in chemical formula 2, and the remaining two are independently CR^aAnd is and

R^aand R¹To R⁷Independently hydrogen, deuterium, substituted or unsubstituted C1 to C10 alkyl, or substituted or unsubstituted C6 to C20 aryl.

According to another embodiment, a composition for an organic photoelectric device includes a first compound for an organic photoelectric device and a second compound for an organic photoelectric device.

The first compound for an organic photoelectric device is the above-described compound for an organic photoelectric device, and the second compound for an organic photoelectric device is represented by chemical formula 3; or a combination of chemical formula 4 and chemical formula 5.

[ chemical formula 3]

In the chemical formula 3, the first and second,

Y¹and Y²Independently a single bond, or a substituted or unsubstituted C6 to C20 arylene group,

Z¹and Z²Independently is a substituted or unsubstituted C6 to C20 aryl, or a substituted or unsubstituted C2 to C30 heterocyclyl, and

R⁸to R¹³Independently hydrogen, deuterium, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C6 to C20 aryl, substituted or unsubstituted C2 to C30 heterocyclyl, cyano, or a combination thereof.

In chemical formula 4 and chemical formula 5,

Z³and Z⁴Independently a substituted or unsubstituted C6 to C20 aryl, or a substituted or unsubstituted C2 to C30 heterocyclyl,

adjacent two of chemical formula 4 are connected to chemical formula 5,

not linked to formula 5 in formula 4 is independently CR^b，

Y³And Y⁴Independently is a single bond, or a substituted or unsubstituted C6 to C20 arylene group, and

R^band R¹⁴To R¹⁷Independently hydrogen, deuterium, cyano, halogen, a substituted or unsubstituted amine group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heterocyclic group.

According to another embodiment, an organic photoelectric device includes an anode and a cathode facing each other, and at least one organic layer between the anode and the cathode, wherein the organic layer contains a compound for an organic photoelectric device or a composition for an organic photoelectric device.

According to other embodiments, a display device including an organic photoelectric device is provided.

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

Drawings

Fig. 1 and 2 are sectional views each showing an organic light emitting diode according to an embodiment.

Detailed Description

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 replaced 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 embodiment of the invention, "substituted" means that at least one hydrogen of the substituent or compound is replaced with deuterium, 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, or cyano. Further, in particular embodiments of the present invention, "substituted" means that at least one hydrogen of the substituent or compound is replaced with deuterium, C1 to C20 alkyl, C6 to C30 aryl, or cyano. Further, in particular embodiments of the present invention, "substituted" means that at least one hydrogen of the substituent or compound is replaced with deuterium, C1 to C5 alkyl, C6 to C18 aryl, or cyano. Further, in particular embodiments of the present invention, "substituted" means that at least one hydrogen of the substituent or compound is replaced with deuterium, cyano, methyl, ethyl, propionyl, butyl, phenyl, biphenyl, terphenyl, or naphthyl.

In the present specification, when a definition is not otherwise provided, "hetero" means that one to three hetero atoms selected from N, O, S, P and Si, and the remaining carbon are contained in one functional group.

In this specification, "aryl" refers to a group including at least one hydrocarbon aromatic moiety, and all elements of the hydrocarbon aromatic moiety have p-orbitals forming conjugates, such as phenyl, naphthyl, and the like, two or more hydrocarbon aromatic moieties may be sigma-linked and may be, for example, biphenyl, terphenyl, quaterphenyl, and the like, and two or more hydrocarbon aromatic moieties are directly or indirectly fused to provide a non-aromatic fused ring, such as 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 in place of carbon (C) in a cyclic compound such as aryl group, cycloalkyl group, condensed ring thereof or combination thereof. When the heterocyclyl is a fused ring, the entire ring or each ring of the heterocyclyl may include one or more heteroatoms.

For example, "heteroaryl" refers 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 include one to three heteroatoms.

More specifically, the substituted or unsubstituted C6 to C30 aryl 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 tetracenyl 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 substituted or unsubstituted anthryl group, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted perylenyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted indenyl group, a substituted or unsubstituted furanyl group, or a combination thereof, but is not limited thereto.

More specifically, the substituted or unsubstituted C2 to C30 heterocyclic group may be a substituted or unsubstituted thiophenyl group, a substituted or unsubstituted pyrrolyl group, a substituted or unsubstituted pyrazolyl group, a substituted or unsubstituted imidazolyl group, a substituted or unsubstituted triazolyl group, a substituted or unsubstituted 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 benzothiophenyl group, a substituted or unsubstituted benzimidazolyl group, a substituted or unsubstituted indolyl group, a substituted or unsubstituted quinolyl group, a substituted or unsubstituted isoquinolyl group, a substituted or unsubstituted quinazolinyl group, a substituted or unsubstituted quinoxalinyl group, A substituted or unsubstituted naphthyridinyl group, a substituted or unsubstituted benzoxazinyl group, a substituted or unsubstituted benzothiazinyl group, a substituted or unsubstituted acridinyl group, a substituted or unsubstituted phenazinyl group, a substituted or unsubstituted phenothiazinyl group, a substituted or unsubstituted phenoxazinyl group, a substituted or unsubstituted carbazolyl 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 characteristic refers to the ability to give electrons to form holes when an electric field is applied according to the Highest Occupied Molecular Orbital (HOMO) level, and the holes formed in the anode can be easily injected into the light emitting layer and transported in the light emitting layer due to the conductive characteristic.

Further, the electron characteristics refer to the ability to accept electrons upon application of an electric field, and electrons formed in the cathode may be easily injected into the light emitting layer and transported in the light emitting layer due to the conductive characteristics, according to the Lowest Unoccupied Molecular Orbital (LUMO) level.

Hereinafter, a compound for an organic photoelectric device according to an embodiment is described.

The compound for an organic photoelectric device according to an embodiment is represented by a combination of chemical formula 1 and chemical formula 2.

In chemical formula 1 and chemical formula 2,

ar is a substituted or unsubstituted C6 to C12 aryl group,

l is a single bond or a substituted or unsubstituted C6 to C20 arylene group,

X¹and X²Independently of each other is O or S,

a of chemical formula 1₁ ^*To a₄ ^*Independently is a linking carbon (C) or CR^a，

A of chemical formula 1₁ ^*To a₄ ^*Are each connected to x in chemical formula 2, and the remaining two are independently CR^aAnd is and

R^aand R¹To R⁷Independently hydrogen, deuterium, substituted or unsubstituted C1 to C10 alkyl, or substituted or unsubstituted C6 to C20 aryl.

The compound represented by the combination of chemical formula 1 and chemical formula 2 includes a triazine core, and a C6 to C12 aryl group of a substituted or unsubstituted 9-carbazolyl group, a substituted or unsubstituted fused dibenzofuran (or fused dibenzothiophene), and a substituted or unsubstituted substituted triazine core.

As described above, by designing a structure in which a triazine core is surrounded by 9-carbazolyl groups, fused dibenzofuran (or fused dibenzothiophene), and C6 to C12 aryl groups, interference of negative ions in an electron transport region can be minimized and device degradation can be solved.

Specifically, a carbazole group substituted for the triazine nucleus is introduced in the N direction to form a C — N bond, thereby causing pi-bond cleavage and preventing expansion of the HOMO electron cloud. This enables efficient positioning and a long life effect can be achieved.

Furthermore, in the case of a fused dibenzofuranyl group (or fused dibenzothiophenyl group) in place of the triazine core, the electron/hole transport capability through the resonant structure is more improved than two dibenzofuran/dibenzothiophene groups connected by σ. In addition, in the case where the fused dibenzofuran/fused dibenzothiophene is compared with the unfused dibenzofuran/dibenzothiophene, the intermolecular attraction increases due to the increase of unshared electron pairs, thereby improving the effect of improving the deposited film. With this effect, device characteristics of low driving and high efficiency and long life can be realized.

Depending on the fusion point, the compound represented by the combination of chemical formula 1 and chemical formula 2 may be represented by, for example, chemical formula 1A to chemical formula 1F.

In chemical formulas 1A to 1F, Ar, L, X¹、X²And R¹To R⁷Is as defined above, and R^a1To R^a4The definition of (A) is the same as that of Ra described above.

In one embodiment, the combination of chemical formula 1 and chemical formula 2 may be represented by chemical formula 1A, and in particular, may be represented by any one of chemical formula 1A-1 to chemical formula 1A-4.

In another embodiment, the combination of chemical formula 1 and chemical formula 2 may be represented by chemical formula 1B, and in particular, may be represented by any one of chemical formula 1B-1 to chemical formula 1B-4.

In another embodiment, the combination of chemical formula 1 and chemical formula 2 may be represented by chemical formula 1C, and in particular, may be represented by any one of chemical formula 1C-1 to chemical formula 1C-4.

In another embodiment, the combination of chemical formula 1 and chemical formula 2 may be represented by chemical formula 1D, and in particular, may be represented by any one of chemical formula 1D-1 to chemical formula 1D-4.

In another embodiment, the combination of chemical formula 1 and chemical formula 2 may be represented by chemical formula 1E, and in particular, may be represented by any one of chemical formula 1E-1 to chemical formula 1E-4.

In another embodiment, the combination of chemical formula 1 and chemical formula 2 may be represented by chemical formula 1F, and in particular, may be represented by any one of chemical formula 1F-1 to chemical formula 1F-4.

In chemical formulas 1A-1 to 1A-4, 1B-1 to 1B-4, 1C-1 to 1C-4, 1D-1 to 1D-4, 1E-1 to 1E-4, and 1F-1 to 1F-4, Ar, L, X¹、X²、R¹To R⁷And R^a1To R^a4The definitions of (a) are the same as above.

In a specific embodiment, the combination of chemical formula 1 and chemical formula 2 may be represented by any one of chemical formula 1A-1 to chemical formula 1A-4, chemical formula 1B-1 to chemical formula 1B-4, chemical formula 1C-2, chemical formula 1C-3, chemical formula 1C-4, chemical formula 1D-1 to chemical formula 1D-4, chemical formula 1E-1 to chemical formula 1E-4, and chemical formula 1F-1 to chemical formula 1F-4.

In a more specific embodiment, the combination of chemical formula 1 and chemical formula 2 may be represented by chemical formula 1B-1, chemical formula 1B-3, chemical formula 1B-4, chemical formula 1C-3, and chemical formula 1F-3.

For example, the combination of chemical formula 1 and chemical formula 2 may be represented by any one of chemical formula 1B-3 and chemical formula 1B-4.

As a specific example, the combination of chemical formula 1 and chemical formula 2 may be represented by chemical formula 1B-1 or chemical formula 1B-4. As described above, when the substitution position of the fused dibenzofuran/fused dibenzothiophene is the No.1 or 4 position, since the fused dibenzofuran/fused dibenzothiophene is included as described above, the electron/hole transport ability is improved, and steric hindrance is maximized at the No.1 or 4 position to reduce the flatness of the molecular structure, so that the structure can be maintained to be close to a sphere. Thus, a deposition surface may be formed while lowering the deposition temperature of molecules and having a higher density on the substrate during deposition.

In one embodiment, X in chemical formula 1¹May be O, and X in chemical formula 2²May be O or S; or, X in chemical formula 1¹May be S, and X in chemical formula 2²May be O or S.

For example, X¹And X²May each be "O".

For example, X¹And X²May each be "S".

For example, X¹May be "O", and X²May be "S".

For example, Ar may be a substituted or unsubstituted phenyl group or a substituted or unsubstituted biphenyl group.

For example, Ar may be a substituted or unsubstituted phenyl group, a substituted or unsubstituted p-biphenylyl group, or a substituted or unsubstituted m-biphenylyl group.

For example, L may be a single bond, or a substituted or unsubstituted phenylene group.

For example, L may be a single bond.

For example, R¹To R⁷And may independently be hydrogen, or substituted or unsubstituted phenyl.

For example, R¹To R⁷Each may be hydrogen.

For example, R^aAnd R^a1To R^a4May each be hydrogen.

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

[ group 1]

A composition for an organic photoelectric device according to another embodiment includes a first compound for an organic photoelectric device and a second compound for an organic photoelectric device.

The first compound for an organic photoelectric device is as described above, and

the second compound for the organic photoelectric device may be represented by chemical formula 3 or a combination of chemical formula 4 and chemical formula 5.

[ chemical formula 3]

In the chemical formula 3, the first and second,

Y¹and Y²Independently a single bond, or a substituted or unsubstituted C6 to C20 arylene group,

Z¹and Z²Independently is a substituted or unsubstituted C6 to C20 aryl, or a substituted or unsubstituted C2 to C30 heterocyclyl, and

R⁸to R¹³Independently hydrogen, deuterium, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C6 to C20 aryl, substituted or unsubstituted C2 to C30 heterocyclyl, cyano, or a combination thereof,

wherein, in chemical formula 4 and chemical formula 5,

Z³and Z⁴Independently a substituted or unsubstituted C6 to C20 aryl, or a substituted or unsubstituted C2 to C30 heterocyclyl,

adjacent two of chemical formula 4 are connected to chemical formula 5,

not linked to formula 5 in formula 4 is independently CR^b，

Y³And Y⁴Independently is a single bond, or a substituted or unsubstituted C6 to C20 arylene group, and

R^band R¹⁴To R¹⁷Independently hydrogen, deuterium, cyano, halogen, substituted or unsubstituted amine group, substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C2 to C30 heterocyclic group.

The second compound of the material having a fast and stable hole transporting property for the organic photoelectric device may be used in the light emitting layer together with the first compound having a fast and stable electron transporting property for the organic photoelectric device to provide charge balance, and thus it may have a high glass transition temperature with respect to molecular weight to provide low driving and long life characteristics.

Depending on the specific attachment point, chemical formula 3 may be represented by, for example, any one of chemical formula 3-1 to chemical formula 3-10.

In chemical formulae 3-1 to 3-10, Y¹、Y²、Z¹、Z²And R⁸To R¹³The definitions of (a) are the same as above.

For example, the second compound for an organic photoelectric device may be represented by chemical formulas 3 to 8.

In an embodiment of the present invention, Z of chemical formula 3¹And Z²May be independently a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted triphenyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted fluorenyl group, or a substituted or unsubstituted pyridyl group, Y¹And Y²May independently be a single bond, a substituted or unsubstituted phenylene group, or a substituted or unsubstituted biphenylene group, and R⁸To R¹³May independently be hydrogen, deuterium, or a substituted or unsubstituted C6 to C12 aryl group.

"substituted" of formula 3 means that at least one hydrogen is replaced with deuterium, C1 to C4 alkyl, C6 to C18 aryl, or C2 to C30 heteroaryl.

For example, -Y in chemical formula 3¹-Z¹and-Y²-Z²May be one of the substituents of group I.

[ group I ]

In group I, is a connection point.

In an embodiment of the invention, -Y¹-Z¹and-Y²-Z²May be any of G-1 to G-4 of group I.

For example, the combination of chemical formula 4 and chemical formula 5 may be made of chemistry depending on the specific fusion point

Any one of formulas 4A to 4E.

In chemical formulas 4A to 4E, Z³And Z⁴、Y³And Y⁴And R¹⁴To R¹⁶As has been described above in the context of the present invention,

R^b1to R^b4And as above for R¹⁴To R¹⁷The same is defined.

For example, the second compound for an organic photoelectric device may be represented by chemical formula 4C or chemical formula 4E.

In an embodiment, Z of chemical formulas 4 and 5³And Z⁴May independently be a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted dibenzothiophenyl group, and

R^b1to R^b4And R¹⁴To R¹⁷May be independently hydrogen, deuterium, cyano, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted pyridyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted dibenzofuranyl, or substituted or unsubstituted dibenzothiophenyl.

In a specific embodiment of the present invention, Z in chemical formulas 4 and 5³And Z⁴And may independently be a substituted or unsubstituted phenyl group, or a substituted or unsubstituted biphenyl group.

In the exemplary implementationIn the formula (II) R^b1To R^b4And R¹⁴To R¹⁷May be independently hydrogen, deuterium, cyano, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted pyridyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted dibenzofuranyl, or substituted or unsubstituted dibenzothiophenyl.

For example, R^b1To R^b4And R¹⁴To R¹⁷May independently be hydrogen, deuterium, cyano, or substituted or unsubstituted phenyl, and

in a particular embodiment, R^b1To R^b4May each be hydrogen, and R¹⁴To R¹⁷And may independently be hydrogen or phenyl.

For example, the compound represented by chemical formula 3 may be one selected from group 2, but is not limited thereto.

[ group 2]

The first compound for an organic photoelectric device and the second compound for an organic photoelectric device may be applied in the form of a composition.

For example, the above-described compound for an organic photoelectric device or composition for an organic photoelectric device may be a host.

The first compound for an organic photoelectric device and the second compound for an organic photoelectric device may be included in a weight ratio of 1:99 to 99: 1. Within the range, a desired weight ratio may be adjusted using electron transport ability of the first compound for the organic photoelectric device and hole transport ability of the second compound for the organic photoelectric device to achieve bipolar characteristics, thereby improving efficiency and lifespan. Within ranges, they may be included, for example, in a weight ratio of about 10:90 to 90:10, about 20:80 to 80:20, e.g., about 20:80 to about 70:30, about 20:80 to about 60:40, or about 20:80 to about 50: 50. For example, they may be included in a weight ratio of 20:80 to 40:60, and for particular embodiments, a weight ratio of 30: 70.

In the composition according to an embodiment of the present invention, the first compound for the organic photoelectric device is one of the above chemical formula 1B-1, chemical formula 1B-3, chemical formula 1B-4, chemical formula 1C-3, and chemical formula 1F-3, and the second compound for the organic photoelectric device may be represented by chemical formula 3-8.

In chemical formula 1B-1, chemical formula 1B-3, chemical formula 1B-4, chemical formula 1C-3, and chemical formula 1F-3, X¹And X²May be independently O or S, Ar may be a substituted or unsubstituted phenyl group, a substituted or unsubstituted p-biphenylyl group, or a substituted or unsubstituted m-biphenylyl group, L may be a single bond, and R¹To R⁷And R^a1To R^a4May each be hydrogen.

In chemical formulas 3 to 8, R⁸To R¹³May each be hydrogen, and

*-Y¹-Z¹and-Y²-Z²May be a substituent of group II.

The above-described compound for an organic photoelectric device or composition for an organic photoelectric device may further include a dopant. The dopant may be, for example, a phosphorescent dopant, such as a red, green, or blue phosphorescent dopant, and may be, for example, a red or green phosphorescent dopant.

The dopant is a material which 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 multiple excitation into a triplet state or more. The dopant may be, for example, an inorganic, organic, or organic/inorganic compound, and one or more types thereof may be used.

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

[ chemical formula Z ]

L¹MX³

In formula Z, M is a metal, and L¹And X³Are identical or different and are ligands which form a coordination compound with M.

M can be, for example, Ir, Pt, Os, Ti, Zr, Hf, Eu, Tb, Tm, Fe, Co, Ni, Ru, Rh, Pd, or combinations thereof, and L¹And X³May be, for example, a bidentate ligand.

The above-described composition for an organic photoelectric device or a composition for an organic photoelectric device may be formed by a dry film forming method such as chemical vapor deposition.

Hereinafter, an organic photoelectric device including a composition to which the above-described compound for an organic photoelectric device or composition for an organic photoelectric device is applied is described.

The organic photoelectric device may be any device that converts electric energy into light energy and vice versa without particular limitation, and may be, for example, an organic optoelectronic device, an organic light emitting diode, an organic solar cell, and an organic photosensitive drum.

Herein, an organic light emitting diode as one embodiment of an organic photoelectric device is described with reference to the accompanying drawings.

Fig. 1 and 2 are sectional views illustrating an organic light emitting diode 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 between the anode 120 and the cathode 110.

The anode 120 may be made of a conductor having a large work function to facilitate hole injection, and may be, for example, a metal oxide, and/or a conductive polymer. For example, the anode 120 may be: such as nickel, platinum,Metals such as vanadium, chromium, copper, zinc, gold, and alloys 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 SnO₂And Sb; conductive polymers such as poly (3-methylthiophene), poly (3,4- (ethylene-1, 2-dioxy) thiophene) (PEDOT), polypyrrole and polyaniline, but are not limited thereto.

The cathode 110 may be made of a conductor having a small work function to assist electron injection, and may be, for example, a metal oxide, and/or a conductive polymer. For example, the cathode 110 may be: metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum silver, tin, lead, cesium, barium, or alloys thereof; materials of multilayer structure, e.g. LiF/Al, LiO₂Al, LiF/Ca, LiF/Al and BaF₂But not limited thereto,/Ca.

The organic layer 105 includes a light emitting layer 130 containing the above compound or composition.

The light emitting layer 130 may include the above-described compound or composition.

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 further increases hole injection and/or hole mobility and blocks 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 hole assist layer 140 may comprise at least one of the compounds of group K, for example.

Specifically, the hole assist layer 140 may include a hole transport layer between the anode 120 and the emission layer 130 and a hole transport assist layer between the emission layer 130 and the hole transport layer, and at least one of the compounds of group K may be included in the hole transport assist layer.

[ group K ]

In the hole transport auxiliary layer, in addition to the compounds, known compounds disclosed in US 5061569A, JP 1993-009471A, WO 1995-009147A1, JP 1995-126615A, JP 1998-095972A and the like, and compounds similar thereto can be used.

In one embodiment, in fig. 1 or 2, the organic light emitting diode may further include an electron transport layer, an electron injection layer, or a hole injection layer as the organic layer 105.

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, and forming the cathode or the anode thereon.

The organic light emitting diode may be applied to an organic light emitting display device.

Hereinafter, embodiments are explained in more detail with reference to examples. However, these embodiments are exemplary, and the scope of the present invention is not limited thereto.

Hereinafter, the raw materials and reactants used in the examples and synthesis examples were purchased from Sigma-Aldrich co.ltd., TCI inc., Tokyo chemical industry, or P & H tech, as long as they were synthesized without specific comments or by a known method.

(preparation of Compound for organic photoelectric device)

Synthesis example 1: synthesis of intermediate I-1

Intermediate I-1 was synthesized by referring to the synthetic method of patent KR 1943030.

HRMS (70eV, EI +): calculated m/z for C24H21BO 4: 384.1533, determining the value: 384.

elemental analysis: c, 75%; h, 6 percent.

Synthesis example 2: synthesis of intermediate I-2

9H-carbazole (100g, 598mmol) and 2- (biphenyl-4-yl) -4, 6-dichloro-1, 3, 5-triazine (271g, 897mmol) available from Tokyo Chemical Industry Co., Ltd are dissolved in 1L of Tetrahydrofuran (THF) under a nitrogen atmosphere, and sodium tert-butoxide (63.2g, 658mmol) is slowly added thereto at 0 ℃ and then stirred. After 12 hours, water was added to the reaction solution, and the mixture was filtered. The obtained residue was isolated by flash column chromatography and purified to obtain intermediate I-2(249g, 96%).

HRMS (70eV, EI +): calculated m/z for C27H17ClN 4: 432.1142, determining the value: 432.

elemental analysis: c, 75%; h, 4 percent.

Synthesis example 3: synthesis of Compound 1

Intermediate I-2(10g, 23.1mmol) was dissolved in 0.1L of toluene under a nitrogen atmosphere, and intermediate I-1(8.88g, 23.1mmol) and tetrakis (triphenylphosphine) palladium (0.27g, 0.23mmol) were added thereto, and then stirred. Subsequently, potassium carbonate (7.98g, 57.8mmol) saturated in water was added thereto, and then heated and refluxed at 100 ℃ for 2 days. When the reaction was completed, water was added to the reaction solution, the mixture was extracted with Dichloromethane (DCM), treated with anhydrous magnesium sulfate to remove water, filtered, and concentrated under reduced pressure. The obtained residue was separated by flash column chromatography and purified to obtain compound 1(7.56g, 50%).

HRMS (70eV, EI +): calculated m/z for C45H26N4O 2: 654.2056, determining the value: 654.

elemental analysis: c, 83%; h, 5 percent.

Synthesis example 4: synthesis of intermediate I-3

Intermediate I-3 was synthesized by referring to the synthesis method of patent KR 1943030.

HRMS (70eV, EI +): calculated m/z for C24H21BO 4: 384.1533, determining the value: 384.

elemental analysis: c, 75%; h, 6 percent.

Synthesis example 5: synthesis of Compound 3

Compound 3(13.0g, 86%) was obtained according to the same method as Synthesis example 3, except that intermediate I-2(10g, 23.1mmol) and intermediate I-3(8.88g, 23.1mmol) were used.

HRMS (70eV, EI +): calculated m/z for C45H26N4O 2: 654.2056, determining the value: 654.

elemental analysis: c, 83%; h, 4 percent.

Synthesis example 6: synthesis of intermediate I-4

Intermediate I-4 was synthesized by reference to the synthesis method of patent KR 1943030.

HRMS (70eV, EI +): calculated m/z for C24H21BO 4: 384.1533, determining the value: 384.

elemental analysis: c, 75%; h, 6 percent.

Synthesis example 7: synthesis of Compound 4

Compound 4(9.68g, 64%) was obtained according to the same method as synthetic example 3, except that intermediate I-2(10g, 23.1mmol) and intermediate I-4(8.88g, 23.1mmol) were used.

HRMS (70eV, EI +): calculated m/z for C45H26N4O 2: 654.2056, determining the value: 654.

elemental analysis: c, 83%; h, 4 percent.

Synthesis example 8: synthesis of intermediate I-5

Dibenzothiophene-4-boronic acid (29.8g, 438mmol) available from Tokyo Chemical Industry co., Ltd was dissolved in 1.0L of Tetrahydrofuran (THF) under a nitrogen atmosphere, and sodium hydroxide (35.0g, 876mmol) was added thereto, and then stirred at 0 ℃. After 30 minutes, 134g of a 30% aqueous solution of hydrogen peroxide were slowly added thereto over 30 minutes. When the reaction was completed, 0.87L of hydrochloric acid having a concentration of 1N was added to the reaction solution, and the mixture was extracted with Ethyl Acetate (EA), treated with anhydrous magnesium sulfate to remove water, filtered, and concentrated under reduced pressure. The obtained residue was isolated by flash column chromatography and purified to obtain intermediate I-5(82.4g, 94%).

HRMS (70eV, EI +): calculated m/z for C12H8 OS: 200.0296, determining the value: 200.

elemental analysis: c, 72%; h, 4 percent.

Synthesis example 9: synthesis of intermediate I-6

Intermediate I-5(80g, 399mmol) was dissolved in 0.8L of N, N-Dimethylformamide (DMF) under a nitrogen atmosphere, and N-bromosuccinimide (71.7g, 399mmol) was slowly added thereto at room temperature, and then stirred for 10 hours. When the reaction was complete, the product was neutralized with sodium thiosulfate saturated in water at 0 ℃. Subsequently, the obtained product was extracted with Dichloromethane (DCM), treated with anhydrous magnesium sulfate to remove water, filtered, and concentrated under reduced pressure. The obtained residue was isolated by flash column chromatography and purified to obtain intermediate I-6(104g, 93%).

HRMS (70eV, EI +): calculated m/z for C12H7 BrOS: 277.9401, determining the value: 278.

elemental analysis: c, 52%; h, 3 percent.

Synthesis example 10: synthesis of intermediate I-7

Intermediate I-7(40.0g, 34%) was obtained according to the same method as in Synthesis example 3, except that intermediate I-6(100g, 358mmol) and 2-chloro-6-fluorophenylboronic acid (75.0g, 430mmol) obtained from Tokyo Chemical Industry Co., Ltd were used.

HRMS (70eV, EI +): calcd for m/z of C18H10 ClFOS: 328.0125, determining the value: 328.

elemental analysis: c, 66%; h, 3 percent.

Synthesis example 11: synthesis of intermediate I-8

Intermediate I-7(38g, 116mmol) was dissolved in 0.4L of N-methyl-2-pyrrolidone (NMP) under a nitrogen atmosphere, and potassium carbonate (22.7g, 231mmol) was added thereto, and then heated and refluxed for 3 hours. When the reaction was completed, after removing the solvent by distillation, water was added to the reaction solution, and the mixture was extracted with Dichloromethane (DCM), treated with anhydrous magnesium sulfate to remove water, filtered, and concentrated under reduced pressure. The obtained residue was isolated by flash column chromatography and purified to obtain intermediate I-8(14.7g, 41%).

HRMS (70eV, EI +): calculated m/z for C18H9 ClOS: 308.0063, determining the value: 308.

elemental analysis: c, 70%; h, 3 percent.

Synthesis example 12: synthesis of intermediate I-9

Intermediate I-8(14g, 45.3mmol) and bis (pinacolato) diboron (13.8g, 54.4mmol), tris (dibenzylideneacetone) dipalladium (0) (0.41g, 0.45mmol) were dissolved in 0.1L of xylene under a nitrogen atmosphere, tricyclohexylphosphine (0.51g, 1.81mmol) and potassium acetate (13.3g, 136mmol) were added thereto, and then heated under reflux for 8 hours. After completion of the reaction, water was added to the reaction solution, the mixture was extracted with Dichloromethane (DCM), treated with anhydrous magnesium sulfate to remove water, filtered, and concentrated under reduced pressure. The obtained residue was isolated by flash column chromatography and purified to obtain intermediate I-9(8.89g, 49%).

HRMS (70eV, EI +): calculated m/z for C24H21BO 3S: 400.1304, determining the value: 400.

elemental analysis: c, 72%; h, 5 percent.

Synthesis example 13: synthesis of Compound 5

Compound 5(7.67g, 55%) was obtained according to the same method as synthetic example 3, except that intermediate I-2(9g, 20.8mmol) and intermediate I-9(8.32g, 20.8mmol) were used.

HRMS (70eV, EI +): calculated m/z for C45H26N4 OS: 670.1827, determining the value: 670.

elemental analysis: c, 81 percent; h, 4 percent.

Synthesis example 14: synthesis of intermediate I-10

Intermediate I-10(133g, 88%) was obtained according to the same method as synthetic example 9, except that 3-methoxybenzenethioether (100g, 648mmol) was purchased from Tokyo Chemical Industry Co., Ltd.

HRMS (70eV, EI +): calculated m/z for C8H9 BrOS: 231.9557, determining the value: 232.

elemental analysis: c, 41%; h, 4 percent.

Synthesis example 15: synthesis of intermediate I-11

Intermediate I-10(130g, 558mmol) was dissolved in 1.3L of Tetrahydrofuran (THF) under nitrogen and then cooled to-78 deg.C. Subsequently, 2.5Mn-BuLi (335mL, 837mmol) dissolved in hexane was slowly added thereto in a dropwise manner over an internal 10 minutes. Then, the obtained mixture was stirred at room temperature for 3 hours. When the reaction was completed, 1n hcl (837mL, 837mmol) was added thereto to neutralize the reaction solution. The obtained mixture was extracted with Ethyl Acetate (EA) and treated with anhydrous magnesium sulfate to remove water, and the residue was washed with hexane and Dichloromethane (DCM) to remove impurities and obtain intermediate I-11(99.5g, 90%).

HRMS (70eV, EI +): calculated m/z for C8H11BO 3S: 198.0522, determining the value: 198.

elemental analysis: c, 49%; h, 6 percent.

Synthesis example 16: synthesis of intermediate I-12

Intermediate I-12(40.0g, 34%) was obtained according to the same method as in Synthesis example 3, except that 3-bromodibenzothiophene (105g, 400mmol) obtained from Tokyo Chemical Industry Co., Ltd. and intermediate I-11(95g, 480mmol) were used.

HRMS (70eV, EI +): calculated m/z for C20H16OS 2: 336.0643, determining the value: 336.

elemental analysis: c, 71%; h, 5 percent.

Synthesis example 17: synthesis of intermediate I-13

Under a nitrogen atmosphere, intermediate I-12(35g, 104mmol) was dissolved in 0.2L of methanol and 0.2L of distilled water, and sodium periodate (33.4g, 156mmol) was added thereto, and then stirred at room temperature for 15 hours. When the reaction was complete, the product was extracted with Dichloromethane (DCM), treated with anhydrous magnesium sulfate to remove water, filtered, and concentrated under reduced pressure. The obtained residue was isolated by flash column chromatography and purified to obtain intermediate I-13(33.0g, 90%).

HRMS (70eV, EI +): calculated m/z for C20H16O2S 2: 352.0592, determining the value: 352.

elemental analysis: c, 68%; h, 5 percent.

Synthesis example 18: synthesis of intermediate I-14

Intermediate I-13(32g, 90.8mmol) was dissolved in 0.3L of Dichloroethane (DCE) under a nitrogen atmosphere, and trifluoromethanesulfonic anhydride (51.2g, 182mmol) was slowly added thereto at 0 ℃, and then stirred at room temperature for 30 minutes. After confirming the total disappearance of intermediate I-13 by thin layer chromatography, 0.06L of pyridine was added thereto, and then stirred at room temperature for 3 hours. After completion of the reaction, water was added to the reaction solution, the mixture was extracted with Dichloromethane (DCM), treated with anhydrous magnesium sulfate to remove water, filtered, and concentrated under reduced pressure. The residue was isolated and purified by flash column chromatography to give intermediate I-14(8.73g, 30%).

HRMS (70eV, EI +): calculated m/z for C19H12OS 2: 320.0330, determining the value: 320.

elemental analysis: c, 71%; h, 4 percent.

Synthesis example 19: synthesis of intermediate I-15

Intermediate I-14(8g, 25.0mmol) and pyridine hydrochloride (14.4g, 125mmol) were added thereto under a nitrogen atmosphere, and then heated and refluxed at 180 ℃ for 3 hours. After completion of the reaction, water was added to the reaction solution, the mixture was extracted with dichloromethane (EA), treated with anhydrous magnesium sulfate to remove water, filtered, and concentrated under reduced pressure. The obtained residue was isolated by flash column chromatography and purified to obtain intermediate I-15(6.20g, 81%).

HRMS (70eV, EI +): calculated m/z for C18H10OS 2: 306.0173, determining the value: 306.

elemental analysis: c, 71%; h, 3 percent.

Synthesis example 20: synthesis of intermediate I-16

Intermediate I-15(6g, 19.6mmol) was dissolved in 0.01L of Dichloromethane (DCM) under nitrogen and then cooled to 0 ℃. Then, trifluoromethanesulfonic anhydride (6.63g, 23.5mmol) was added thereto, and then stirred. After 3 hours, the reaction solution was cooled to 0 ℃, water was slowly added thereto for 30 minutes, and the mixture was extracted with Dichloromethane (DCM), treated with anhydrous magnesium sulfate to remove water, filtered, and concentrated under reduced pressure. The obtained residue was isolated by flash column chromatography and purified to obtain intermediate I-16(8.42g, 98%).

HRMS (70eV, EI +): calculated m/z for C19H9F3O3S 3: 437.9666, determining the value: 438.

elemental analysis: c, 52%; h, 2 percent.

Synthesis example 21: synthesis of intermediate I-17

Except for intermediate I-16, intermediate I-17(3.19g, 42%) was obtained according to the same procedure as the palladium-catalyzed synthesis of the borylation of an aryl halide or triflate with a dialkoxyborane: a Novel and simple Route to arylborates is described (A Novel and simple Synthetic Route to Arylboronates) as described in journal of organic chemistry 65(1), 164-; 200.

HRMS (70eV, EI +): calculated m/z for C24H21BO2S 2: 416.1076, determining the value: 416.

elemental analysis: c, 69%; h, 5 percent.

Synthesis example 22: synthesis of Compound 9

Compound 9(3.96g, 80%) was obtained according to the same method as synthetic example 3, except that intermediate I-2(3.12g, 7.21mmol) and intermediate I-17(3g, 7.21mmol) were used.

HRMS (70eV, EI +): calculated m/z for C45H26N4S 2: 686.1599, determining the value: 686.

elemental analysis: c, 79%; h, 4 percent.

Synthesis example 23: synthesis of intermediate I-18

Intermediate I-18(238g, 92%) was obtained according to the same method as in synthesis example 2, except that 9H-carbazole (100g, 598mmol) and 2- (biphenyl-3-yl) -4, 6-dichloro-1, 3, 5-triazine (271g, 897mmol) available from Tokyo Chemical Industry co., Ltd were used.

HRMS (70eV, EI +): calculated m/z for C27H17ClN 4: 432.1142, determining the value: 432.

elemental analysis: c, 75%; h, 4 percent.

Synthesis example 24: synthesis of Compound 17

Compound 17(13.0g, 86%) was obtained according to the same method as synthetic example 3, except that intermediate I-18(10g, 23.1mmol) and intermediate I-11(8.88g, 23.1mmol) were used.

HRMS (70eV, EI +): calculated m/z for C45H26N4O 2: 654.2056, determining the value: 654.

elemental analysis: c, 83%; h, 4 percent.

Synthesis example 25: synthesis of intermediate I-19

Compound I-19(26.6g, 76%) was obtained according to the same method as synthetic example 3 except that intermediate I-1(30g, 78.1mmol) and 2, 4-dichloro-6-phenyl-1, 3, 5-triazine (26.5g, 117mmol) were used.

HRMS (70eV, EI +): calculated m/z for C27H14ClN3O 2: 447.0775, determining the value: 447.

elemental analysis: c, 72%; h, 3 percent.

Synthesis example 26: synthesis of intermediate I-20

Intermediate I-20(23.7g, 80%) was obtained according to the same method as in synthesis example 3, except that 1-bromo-9H-carbazole (30g, 122mmol) and phenylboronic acid (16.3g, 134mmol) were used.

HRMS (70eV, EI +): calculated m/z for C18H 13N: 243.1048, determining the value: 243.

elemental analysis: c, 89%; h, 5 percent.

Synthesis example 27: synthesis of Compound 49

Intermediate I-20(10g, 41.1mmol) and intermediate I-19(22.1g, 49.3mmol), tris (diphenyleneacetone) dipalladium (0) (1.13g, 1.23mmol) were dissolved in 0.1L of xylene under a nitrogen atmosphere, to which tri-tert-butylphosphine (1.0g, 4.93mmol) and sodium tert-butoxide (4.74g, 49.3mmol) were added in this order, and then heated and refluxed at 130 ℃ for 16 hours. After completion of the reaction, water was added to the reaction solution, the mixture was extracted with Dichloromethane (DCM), treated with anhydrous magnesium sulfate to remove water, filtered, and concentrated under reduced pressure. The obtained residue was separated by flash column chromatography and purified to obtain compound 49(16.4g, 61%).

HRMS (70eV, EI +): calculated m/z for C45H26N4O 2: 654.2056, determining the value: 654.

elemental analysis: c, 83%; h, 4 percent.

Synthesis example 28: synthesis of Compound 193

Compound 193(21.6g, 95%) was obtained according to the same method as in synthetic example 27, except that 3- (9H-carbazol-9-yl) phenylboronic acid (10g, 34.8mmol) obtained from Tokyo Chemical Industry co., ltd. and intermediate I-19(18.7g, 41.8mmol) were used.

HRMS (70eV, EI +): calculated m/z for C45H26N4O 2: 654.2056, determining the value: 654.

elemental analysis: c, 83%; h, 4 percent.

Synthesis example 29: synthesis of intermediate I-20

Intermediate I-20 was synthesized by referring to the synthetic method of patent KR 2019-0110775.

HRMS (70eV, EI +): calculated m/z for C24H21BO 4: 384.1533, determining the value: 384.

elemental analysis: c, 75%; h, 6 percent.

Synthesis example 30: synthesis of Compound 273

Compound 273(15.1g, 97%) was obtained according to the same method as synthetic example 3 except for using intermediate I-2(10g, 23.1mmol) and intermediate I-20(8.88g, 23.1 mmol).

HRMS (70eV, EI +): calculated m/z for C45H26N4O 2: 654.2056, determining the value: 654.

elemental analysis: c, 83%; h, 4 percent.

Synthesis example 31: synthesis of intermediate I-21

Intermediate I-21 was synthesized by reference to the synthetic method of patent KR 2019-0110775.

HRMS (70eV, EI +): calculated m/z for C24H21BO 4: 384.1533, determining the value: 384.

elemental analysis: c, 75%; h, 6 percent.

Synthesis example 32: synthesis of Compound 275

Compound 275(14.4g, 95%) was obtained according to the same method as in Synthesis example 3, except that intermediate I-2(10g, 23.1mmol) and intermediate I-21(8.88g, 23.1mmol) were used.

HRMS (70eV, EI +): calculated m/z for C45H26N4O 2: 654.2056, determining the value: 654.

elemental analysis: c, 83%; h, 4 percent.

Synthesis example 33: synthesis of Compound HT2

Compound HT2 was synthesized by reference to the synthesis method of patent EP 3034581.

HRMS (70eV, EI +): calculated m/z for C42H28N 2: 560.2252, determining the value: 560.

elemental analysis: c, 90%; h, 5 percent.

Synthesis example 34: synthesis of Compound HT5

Compound HT5 was synthesized by reference to the synthetic methods of patent KR 10-2019-0000597.

HRMS (70eV, EI +): calculated m/z for C48H32N 2: 636.2565, determining the value: 636.

elemental analysis: c, 91%; h, 5 percent.

Synthesis example 35: synthesis of Compound HT6

Compound HT5 was synthesized by reference to the synthesis method of patent EP 2947071.

HRMS (70eV, EI +): calculated m/z for C48H32N 2: 636.2565, determining the value: 636.

elemental analysis: c, 91%; h, 5 percent.

Synthesis example 36: synthesis of Compound HT41

Compound HT41 was synthesized by reference to the synthesis method of patent KR 2031300.

HRMS (70eV, EI +): calculated m/z for C42H28N 2: 560.2252, determining the value: 560.

elemental analysis: c, 90%; h, 5 percent.

Synthesis example 37: synthesis of Compound HT47

Compound HT47 was synthesized by reference to the synthetic method of patent WO 2018-095391.

HRMS (70eV, EI +): calculated m/z for C48H32N 2: 636.2565, determining the value: 636.

elemental analysis: c, 91%; h, 5 percent.

Synthesis example 38: synthesis of Compound host 1

Compound body 1 was synthesized by referring to the synthesis method of patent KR 1943030.

HRMS (70eV, EI +): calculated m/z for C33H19N3O 2: 489.1477, determining the value: 489.

elemental analysis: c, 81 percent; h, 4 percent.

Synthesis example 39: synthesis of Compound host 2

Compound body 2 was synthesized by referring to the synthesis method of patent KR 1943030.

HRMS (70eV, EI +): calculated m/z for C33H19N3O 2: 489.1477, determining the value: 489.

elemental analysis: c, 81 percent; h, 4 percent.

Synthesis example 40: synthesis of Compound host 3

Compound body 3 was synthesized by referring to the synthesis method of patent KR 1943030.

HRMS (70eV, EI +): calculated m/z for C39H21N3O 3: 579.1583, determining the value: 579.

elemental analysis: c, 81 percent; h, 4 percent.

Synthesis example 41: synthesis of Compound host 4

Compound body 4 was synthesized by referring to the synthesis method of patent KR 1943030.

HRMS (70eV, EI +): calculated m/z for C39H21N3O 3: 579.1583, determining the value: 579.

elemental analysis: c, 81 percent; h, 4 percent.

Synthesis example 42: synthesis of Compound host 5

Compound body 5 was synthesized by the synthetic method of reference patent KR 2011-0013445.

HRMS (70eV, EI +): calculated m/z for C52H31N3O 2: 729.2416, determining the value: 729.

elemental analysis: c, 86 percent; h, 4 percent.

Manufacture of organic light emitting diodes

Example 1

The glass substrate coated with ITO (indium tin oxide) was washed with distilled water and ultrasonic waves. After washing with distilled water, the glass substrate was ultrasonically washed with a solvent (such as isopropyl alcohol, acetone, methanol, etc.) and dried, and then moved to a plasma cleaner, oxygen plasma cleaned for 10 minutes, and moved to a vacuum depositor. Using the ITO transparent electrode thus obtained as an anode, Compound A doped with 1% NDP-9 (available from Novaled) was vacuum-deposited on an ITO substrate to form

A thick hole transport layer, and depositing a compound B on the hole transport layer to form

A thick hole transport assist layer. On the hole transport layer, a hole transport layer was formed by using compound 1 and compound HT2 of synthesis example 3 as hosts and doping 10 wt% of PhGD as a dopant

A thick light emitting layer. Herein, compound 1 and compound HT2 were used in a 3:7 ratio. Subsequently, compound C is deposited on the light-emitting layer to form

A thick electron transport auxiliary layer, and simultaneously vacuum depositing compound D and Liq at a ratio of 1:1 to form

A thick electron transport layer. Mixing LiQ

And Al

And sequentially vacuum-depositing on the electron transport layer to form a cathode, thereby fabricating an organic light emitting diode.

ITO/compound a (1% NDP-9 doped,

) Compound B

EML [ Compound 1: compounds HT2(3:7) and PhGD 10 wt%)]

Compound C

Compound D: LiQ

/LiQ

/Al

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

Compound B: n, N-bis (9, 9-dimethyl-9H-fluoren-4-yl) -9, 9-spirobi (fluoren) -2-amine

Compound C: 2- (3- (3- (9, 9-dimethyl-9H-fluoren-2-yl) phenyl) -4, 6-diphenyl-1, 3, 5-triazine

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

[PhGD]

Examples 2 to 16 and comparative examples 1 to 5

A diode was manufactured in the same manner as in example 1, except that the composition was changed to the composition shown in table 1 instead of compound 1 and compound HT 2.

Evaluation of

The organic light emitting diodes according to examples 1 to 16 and comparative examples 1 to 5 were evaluated for driving voltage, light emitting efficiency, and life span characteristics.

Specific measurement methods are as follows, and the results are shown in table 1.

(1) Measurement of current density variations depending on voltage variations

The obtained organic light emitting diode was measured with respect to a current value flowing in the unit device while increasing the voltage from 0V to 10V using a current-voltage meter (Keithley 2400), and the measured current value was divided by an area to provide a result.

(2) Measurement of brightness variation depending on voltage variation

When the voltage of the organic light emitting diode was increased from 0V to 10V, the luminance was measured using a luminance meter (Minolta Cs-1000A).

(3) Measurement of luminous efficiency

By using the luminance and current density and voltage of the items (1) and (2), the luminance and current density at the same current density (10 mA/cm) were calculated²) Current efficiency (cd/A).

(4) Measurement of lifetime

By measuring the time for the current efficiency (cd/A) to decrease to 97%, while the luminance (cd/m) is measured²) Maintained at 24000cd/m²To obtain a result.

(Table 1)

Referring to table 1, the organic light emitting diodes according to examples 1 to 16 have significantly improved driving voltage, light emitting efficiency, and life span characteristics, as compared to the organic light emitting diodes according to comparative examples 1 to 5.

While the invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not to be limited to the disclosed embodiments, but on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.

Description of the symbols

100. 200: organic light emitting diode

105: organic layer

110: cathode electrode

120: anode

130: luminescent layer

140: a hole assist layer.

Claims (16)

1. A compound for an organic photoelectric device, represented by a combination of chemical formula 1 and chemical formula 2:

wherein, in chemical formula 1 and chemical formula 2,

ar is a substituted or unsubstituted C6 to C12 aryl group,

l is a single bond or a substituted or unsubstituted C6 to C20 arylene group,

X¹and X²Independently of each other is O or S,

a of chemical formula 1₁ ^*To a₄ ^*Independently is a linking carbon (C) or CR^a，

A of chemical formula 1₁ ^*To a₄ ^*Two adjacent of (a) are each linked to x in chemical formula 2, and the remaining two are independently CR^aAnd is and

R^aand R¹To R⁷Independently hydrogen, deuterium, substituted or unsubstituted C1 to C10 alkyl, or substituted or unsubstituted C6 to C20 aryl.

2. The compound according to claim 1, wherein the combination of chemical formula 1 and chemical formula 2 is represented by any one of chemical formula 1A to chemical formula 1F:

wherein, in chemical formulas 1A to 1F,

Ar、L、X¹、X²and R¹To R⁷Is as defined in claim 1, and Ra¹To Ra⁴Is defined as in claim 1^aThe same is true.

3. The compound according to claim 1, wherein the combination of chemical formula 1 and chemical formula 2 is represented by any one of chemical formula 1B-1, chemical formula 1B-3, chemical formula 1B-4, chemical formula 1C-3, and chemical formula 1F-3:

wherein, in chemical formula 1B-1, chemical formula 1B-3, chemical formula 1B-4, chemical formula 1C-3 and chemical formula 1F-3,

Ar、L、X¹、X²and R¹To R⁷Is as defined in claim 1, and Ra¹To Ra⁴Is defined as in claim 1^aThe same is true.

4. The compound according to claim 3, wherein the combination of chemical formula 1 and chemical formula 2 is represented by any one of chemical formula 1B-1, chemical formula 1B-3, and chemical formula 1B-4.

5. The compound according to claim 3, wherein the combination of chemical formula 1 and chemical formula 2 is represented by chemical formula 1B-1 or chemical formula 1B-4.

6. The compound of claim 1, wherein,

x in chemical formula 1¹Is O, and X in chemical formula 2²Is O or S; or

X in chemical formula 1¹Is S, and X in chemical formula 2²Is S.

7. The compound according to claim 1, wherein X in chemical formula 1¹Is O, and X in chemical formula 2²Is O or S.

8. The compound of claim 1, wherein,

ar is a substituted or unsubstituted phenyl group, or a substituted or unsubstituted biphenyl group,

l is a single bond, or a substituted or unsubstituted phenylene group,

R¹to R⁷Independently is hydrogen, or substituted or unsubstituted phenyl, and

R^aeach is hydrogen.

9. The compound of claim 1, which is one selected from group 1:

[ group 1]

10. A composition for use in an organic optoelectronic device comprising

A first compound for an organic photoelectric device and a second compound for an organic photoelectric device,

wherein the first compound for an organic photoelectric device is the compound for an organic photoelectric device according to claim 1, and

the second compound for an organic photoelectric device is represented by chemical formula 3; or a combination of chemical formula 4 and chemical formula 5:

wherein, in chemical formula 3,

Y¹and Y²Independently a single bond, or a substituted or unsubstituted C6 to C20 arylene group,

Z¹and Z²Independently is a substituted or unsubstituted C6 to C20 aryl, or a substituted or unsubstituted C2 to C30 heterocyclyl, and

R⁸to R¹³Independently hydrogen, deuterium, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C6 to C20 aryl, substituted or unsubstituted C2 to C30 heterocyclyl, cyano, or a combination thereof,

wherein, in chemical formula 4 and chemical formula 5,

Z³and Z⁴Independently a substituted or unsubstituted C6 to C20 aryl, or a substituted or unsubstituted C2 to C30 heterocyclyl,

adjacent two of chemical formula 4 are connected to chemical formula 5,

not linked to formula 5 in formula 4 is independently CR^b，

Y³And Y⁴Independently is a single bond, or a substituted or unsubstituted C6 to C20 arylene group, and

R^band R¹⁴To R¹⁷Independently hydrogen, deuterium, cyano, halogen, substituted or unsubstituted amine group, substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C2 to C30 heterocyclic group.

11. The composition of claim 10, wherein chemical formula 3 is represented by chemical formulae 3-8:

wherein, in chemical formulas 3 to 8,

Y¹、Y²、Z¹、Z²and R⁸To R¹³Is as defined in claim 10.

12. The composition according to claim 10, wherein x-Y in chemical formula 3¹-Z¹and-Y²-Z²Is one of the substituents of group I:

[ group I ]

Wherein, in group I, is a connection point.

13. The composition according to claim 10, wherein,

the first compound for an organic photoelectric device is represented by any one of chemical formula 1B-1, chemical formula 1B-3, chemical formula 1B-4, chemical formula 1C-3, and chemical formula 1F-3, and

the second compound for an organic photoelectric device is represented by chemical formulas 3 to 8:

wherein, in chemical formula 1B-1, chemical formula 1B-3, chemical formula 1B-4, chemical formula 1C-3 and chemical formula 1F-3,

X¹and X²Independently of each other is O or S,

ar is a substituted or unsubstituted phenyl group, a substituted or unsubstituted p-biphenylyl group, or a substituted or unsubstituted m-biphenylyl group,

l is a single bond, and

R¹to R⁷And R^a1To R^a4Each is hydrogen;

wherein, in chemical formulas 3 to 8,

R⁸to R¹³Each is hydrogen, and

y in chemical formula 3¹-Z¹and-Y²-Z²Is one of the substituents of group I,

[ group I ]

Wherein, in group I, is a connection point.

14. An organic photoelectric device comprises

An anode and a cathode facing each other, and

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

wherein the organic layer contains the compound for an organic photoelectric device according to any one of claim 1 to claim 9; or the composition for an organic photoelectric device according to any one of claims 10 to 13.

15. The organic optoelectronic device of claim 14,

the organic layer includes a light emitting layer, and

the light-emitting layer includes the compound for an organic photoelectric device or the composition for an organic photoelectric device.

16. A display device comprising the organic photoelectric device according to claim 14.

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