WO2024005500A1 - Compound for organic optoelectronic diode, organic optoelectronic diode, and display device - Google Patents

Abstract

The present invention relates to: a compound for an organic optoelectronic diode, represented by chemical formula 1; and an organic optoelectronic diode and a display device, comprising same. The details of chemical formula 1 are as defined in the specification.

Description

Compounds for organic optoelectronic devices, organic optoelectronic devices and display devices

It relates to compounds for organic optoelectronic devices, organic optoelectronic devices, and display devices.

An organic optoelectronic diode is a device that can mutually convert electrical energy and light energy.

Organic optoelectronic devices can be broadly divided into two types depending on their operating principles. One is a photoelectric device that generates electrical energy by separating exciton formed by light energy into electrons and holes and transferring the electrons and holes to different electrodes, and the other is a photoelectric device that generates electrical energy by supplying voltage or current to the electrode. It is a light emitting device that generates light energy from.

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

Among these, organic light emitting diodes (OLEDs) have recently received great attention due to the increased demand for flat panel display devices. Organic light emitting devices are devices that convert electrical energy into light, and the performance of organic light emitting devices is greatly influenced by the organic materials located between electrodes.

One embodiment provides a compound for an organic optoelectronic device that can implement a highly efficient and long-life organic optoelectronic device.

Another embodiment provides an organic optoelectronic device including the compound for an organic optoelectronic device.

Another embodiment provides a display device including the organic optoelectronic device.

According to one embodiment, a compound for an organic optoelectronic device represented by the following formula (1) is provided.

[Formula 1]

In Formula 1,

Ar ¹ and Ar ² are each independently a substituted or unsubstituted C1 to C10 alkyl group or a substituted or unsubstituted C6 to C20 aryl group,

Ar ³ is a substituted or unsubstituted C6 to C30 aryl group or a substituted or unsubstituted C2 to C30 heterocyclic group,

R ¹ to R ⁶ are each independently hydrogen, deuterium, halogen group, cyano group, substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C6 to C30 aryl group, or substituted or unsubstituted C6 to C30 heterocycle. It is a spirit,

n1, n3, n5 and n6 are each independently an integer from 1 to 4,

n2 is one of the integers from 1 to 3,

n4 is one of the integers from 1 to 5.

According to another embodiment, an organic optoelectronic device is provided, including an anode and a cathode facing each other, and at least one organic layer located between the anode and the cathode, wherein the organic layer includes the compound for an organic optoelectronic device.

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

High-efficiency, long-life organic optoelectronic devices can be realized.

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

<Explanation of symbols>

100: Organic light emitting device

105: Organic layer

110: cathode

120: anode

130: light emitting layer

140: hole transport area

150: electron transport area

Hereinafter, embodiments of the present invention will be described in detail. However, this is presented as an example, and the present invention is not limited thereby, and the present invention is only defined by the scope of the claims to be described later.

In this specification, unless otherwise defined, “substitution” means that at least one hydrogen in the substituent or compound is deuterium, halogen group, hydroxyl group, amino group, substituted or unsubstituted C1 to C30 amine group, nitro group, substituted or Unsubstituted C1 to C40 silyl group, C1 to C30 alkyl group, C1 to C10 alkylsilyl group, C6 to C30 arylsilyl group, C3 to C30 cycloalkyl group, C3 to C30 heterocycloalkyl group, C6 to C30 aryl group, C2 to C30 It means substituted with a heteroaryl group, C1 to C20 alkoxy group, C1 to C10 trifluoroalkyl group, cyano group, or a combination thereof.

In one example of the present invention, "substitution" means that at least one hydrogen in the substituent or compound is deuterium, C1 to C30 alkyl group, C1 to C10 alkylsilyl group, C6 to C30 arylsilyl group, C3 to C30 cycloalkyl group, C3 to C30 It means substituted with a heterocycloalkyl group, a C6 to C30 aryl group, a C2 to C30 heteroaryl group, or a cyano group. Additionally, in a specific example of the present invention, “substitution” means that at least one hydrogen in a substituent or compound is replaced with deuterium, a C1 to C20 alkyl group, a C6 to C30 aryl group, or a cyano group. Additionally, in a specific example of the present invention, “substitution” means that at least one hydrogen in a substituent or compound is replaced with deuterium, a C1 to C5 alkyl group, a C6 to C18 aryl group, or a cyano group. In addition, in a specific example of the present invention, "substitution" means replacing at least one hydrogen in a substituent or compound with deuterium, cyano group, methyl group, ethyl group, propyl group, butyl group, phenyl group, biphenyl group, terphenyl group, or naphthyl group. It means that it has been done.

In this specification, “unsubstituted” means that a hydrogen atom remains a hydrogen atom without being substituted with another substituent.

As used herein, “hydrogen substitution (-H)” may include “deuterium substitution (-D)” or “tritium substitution (-T)”.

As used herein, unless otherwise defined, “hetero” means that one functional group contains 1 to 3 heteroatoms selected from the group consisting of N, O, S, P, and Si, and the remainder is carbon. .

In this specification, “aryl group” is a general concept of a group having one or more hydrocarbon aromatic moieties. All elements of the hydrocarbon aromatic moiety have p-orbitals, and these p-orbitals are conjugated. A form in which two or more hydrocarbon aromatic moieties are connected through a sigma bond, such as a biphenyl group, a terphenyl group, a quarterphenyl group, etc., and two or more hydrocarbon aromatic moieties. It may include a non-aromatic fused ring to which they are directly or indirectly fused, such as a fluorenyl group.

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

In this specification, “heterocyclic group” is a higher concept including heteroaryl group, and in ring compounds such as aryl group, cycloalkyl group, fused ring thereof, or combination thereof, N, O, instead of carbon (C) It means containing at least one hetero atom selected from the group consisting of S, P and Si. When the heterocyclic group is a fused ring, the entire heterocyclic group or each ring may contain one or more heteroatoms.

As an example, “heteroaryl group” means that the aryl group contains at least one hetero atom selected from the group consisting of N, O, S, P, and Si. Two or more heteroaryl groups may be directly connected through a sigma bond, or when the heteroaryl group includes two or more rings, the two or more rings may be fused to each other. When the heteroaryl group is a fused ring, each ring may contain 1 to 3 heteroatoms.

More specifically, the substituted or unsubstituted C6 to C30 aryl group is 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 Unsubstituted naphthacenyl group, substituted or unsubstituted pyrenyl group, substituted or unsubstituted biphenyl group, substituted or unsubstituted p-terphenyl group, substituted or unsubstituted m-terphenyl group, substituted or unsubstituted o- Terphenyl group, substituted or unsubstituted chrysenyl group, substituted or unsubstituted benzophenanthrenyl group, substituted or unsubstituted triphenylene group, substituted or unsubstituted perylenyl group, substituted or unsubstituted fluorenyl group, substituted Or it may be an unsubstituted indenyl group, or a combination thereof, but is not limited thereto.

More specifically, the substituted or unsubstituted C2 to C30 heterocyclic group includes a substituted or unsubstituted furanyl group, a substituted or unsubstituted thiophenyl group, a substituted or unsubstituted pyrrolyl group, a substituted or unsubstituted pyrazolyl group, or a substituted or unsubstituted pyrazolyl group. Or unsubstituted imidazolyl group, substituted or unsubstituted triazolyl group, substituted or unsubstituted oxazolyl group, substituted or unsubstituted thiazolyl group, substituted or unsubstituted oxadiazolyl group, substituted or unsubstituted Thiadiazolyl group, substituted or unsubstituted pyridyl group, substituted or unsubstituted pyrimidinyl group, substituted or unsubstituted pyrazinyl group, substituted or unsubstituted triazinyl group, substituted or unsubstituted benzofuranyl group, substituted Or unsubstituted benzothiophenyl group, substituted or unsubstituted benzimidazolyl group, substituted or unsubstituted indolyl group, substituted or unsubstituted quinolinyl group, substituted or unsubstituted isoquinolinyl group, substituted or unsubstituted Quinazolinyl group, substituted or unsubstituted quinoxalinyl group, substituted or unsubstituted naphthyridinyl group, substituted or unsubstituted benzoxazinyl group, substituted or unsubstituted benzothiazinyl group, substituted or unsubstituted acridinyl group , substituted or unsubstituted phenazinyl group, substituted or unsubstituted phenothiazinyl group, substituted or unsubstituted phenoxazinyl group, substituted or unsubstituted carbazolyl group, substituted or unsubstituted dibenzofuranyl group, or substituted or unsubstituted dibenzothiophenyl group, substituted or unsubstituted benzonaphtufuranyl group, substituted or unsubstituted benzonaphthothiophenyl group, substituted or unsubstituted benzofuranofluorenyl group, substituted or unsubstituted benzo It may be a thiophenefluorenyl group or a combination thereof, but is not limited thereto.

In this specification, the hole characteristic refers to the characteristic of forming a hole by donating electrons when an electric field is applied. It has conduction characteristics according to the HOMO level and injects holes formed at the anode into the light-emitting layer. It refers to a characteristic that facilitates the movement of holes formed in the anode and in the light emitting layer.

In addition, electronic properties refer to the property of being able to receive electrons when an electric field is applied, and have conduction properties along the LUMO level, such as injection of electrons formed at the cathode into the light-emitting layer, movement of electrons formed in the light-emitting layer to the cathode, and movement of electrons from the light-emitting layer. It refers to a characteristic that facilitates movement.

Hereinafter, a compound for an organic optoelectronic device according to an embodiment will be described.

A compound for an organic optoelectronic device according to one embodiment is represented by the following formula (1).

[Formula 1]

In Formula 1,

Ar ¹ and Ar ² are each independently a substituted or unsubstituted C1 to C10 alkyl group or a substituted or unsubstituted C6 to C20 aryl group,

Ar ³ is a substituted or unsubstituted C6 to C30 aryl group or a substituted or unsubstituted C2 to C30 heterocyclic group,

R ¹ to R ⁶ are each independently hydrogen, deuterium, halogen group, cyano group, substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C6 to C30 aryl group, or substituted or unsubstituted C6 to C30 heterocycle. It is a spirit,

n1, n3, n5 and n6 are each independently an integer from 1 to 4,

n2 is one of the integers from 1 to 3,

n4 is one of the integers from 1 to 5.

The compound represented by Formula 1 has a structure in which the amine core is substituted with dibenzosilol, diphenylfluorene, and an aryl group (or heteroaryl group), and the planarity of the molecule increases, improving the stacking of the lattice, thereby increasing the glass transition temperature. and hole mobility increases.

Since the dibenzosilol has high heat resistance and fast hole transport ability, it is advantageous for lowering the driving voltage, increasing power efficiency, and implementing devices with excellent lifespan characteristics.

Since the diphenylfluorene has little electrical and electronic interaction with adjacent molecules due to its molecular size, electrical and electronic interaction with adjacent layers can be reduced, and thus a device with improved device lifespan and efficiency can be implemented.

In addition, since dibenzosilol and diphenylfluorene are included at the same time, the movement of molecules is limited, resulting in a high glass transition temperature, which prevents deterioration of device performance due to Joule heat generated during operation.

In particular, dibenzosilol is oriented in the para configuration as it is substituted with an amine at position 3, and in this case, compared to the meta configuration, HOMO is located throughout the dibenzosilol structure, which favors hole movement between molecules and lowers the driving voltage of the device. Lifespan can be improved.

As an example, a comparison of the optimized structure of the molecule and the resulting HOMO electron cloud according to the para orientation, in which an amine is substituted in the 3-position of dibenzosilol, and the meta orientation, in which an amine is substituted in the 2-position of dibenzosilol, is described below. It is the same as what was said.

It can be seen that the para orientation of dibenzosilol significantly improves hole mobility compared to the meta orientation of dibenzosilol, resulting in improved driving voltage, efficiency, and lifespan.

The above Chemical Formula 1 may be represented by any of the following Chemical Formulas 1-I to 1-III depending on the connection point between the amine and diphenylfluorene.

[Formula 1-Ⅰ] [Formula 1-Ⅱ] [Formula 1-Ⅲ]

In Formula 1-I to Formula 1-III,

Ar ¹ to Ar ³ , R ¹ to R ⁶ , and n1 to n6 are as described above.

For example, Ar ³ is 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, or a substituted or unsubstituted group. phenanthrenyl group, substituted or unsubstituted chrysenyl group, substituted or unsubstituted fluorenyl group, substituted or unsubstituted triphenylene group, substituted or unsubstituted dibenzofuranyl group, substituted or unsubstituted dibenzothi It may be an openyl group or a substituted or unsubstituted dibenzosilolyl group.

As a specific example, Ar ³ is a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted dibenzofuranyl group. Alternatively, it may be an unsubstituted dibenzothiophenyl group or a substituted or unsubstituted dibenzosilolyl group.

For example, Ar ³ may be selected from the substituents listed in Group I below, but is not limited thereto.

[Group Ⅰ]

As an example, Ar ¹ and Ar ² may each independently be a substituted or unsubstituted C1 to C5 alkyl group or a substituted or unsubstituted C6 to C12 aryl group.

For example, Ar ¹ and Ar ² may each independently be a substituted or unsubstituted methyl group, or a substituted or unsubstituted phenyl group.

As an example, R ¹ to R ⁶ may each independently be hydrogen, deuterium, a halogen group, a cyano group, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group.

For example, R ¹ to R ⁶ may each independently be hydrogen, deuterium, a halogen group, a cyano group, a substituted or unsubstituted C1 to C5 alkyl group, or a substituted or unsubstituted C6 to C12 aryl group.

As a more specific example, R ¹ to R ⁶ are each independently hydrogen, deuterium, a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted n-propyl group, or a substituted or unsubstituted iso-propyl group. It may be a substituted or unsubstituted n-butyl group, a substituted or unsubstituted tert-butyl group, or a substituted or unsubstituted phenyl group.

For example, Formula 1 may be selected from the following Formulas 1-1 to 1-6, but is not limited thereto.

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

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

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

In Formulas 1-1 to 1-6,

Ar ¹ to Ar ³ , R ¹ to R ⁶ , and n2 to n6 are as described above,

n1', n3', n5', and n6' are each independently integers of 1 or 2.

For example, Formula 1 may be selected from Formula 2-1 to Formula 2-9 below, but is not limited thereto.

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

[Formula 2-4] [Formula 2-5] [Formula 2-6]

[Formula 2-7] [Formula 2-8] [Formula 2-9]

In Formulas 2-1 to 2-9, Ar ¹ to Ar ³ are as described above.

For example, the compound for an organic optoelectronic device represented by Formula 1 may include, but is not limited to, the compounds listed in Group 1 below.

[Group 1]

compound	core structure	Ar 1 and Ar 2	Ar 3	compound	core structure	Ar 1 and Ar 2	Ar 3
1-1	chemical formula 2-1	methyl group	I-1	1-19	chemical formula 2-1	methyl group	I-19
1-2			I-2	1-20			I-20
1-3			I-3	1-21			I-21
1-4			I-4	1-22			I-22
1-5			I-5	1-23			I-23
1-6			I-6	1-24			I-24
1-7			I-7	1-25			I-25
1-8			I-8	1-26			I-26
1-9			I-9	1-27			I-27
1-10			I-10	1-28			I-28
1-11			I-11	1-29			I-29
1-12			I-12	1-30			I-30
1-13			I-13	1-31			I-31
1-14			I-14	1-32			I-32
1-15			I-15	1-33			I-33
1-16			I-16	1-34			I-34
1-17			I-17	1-35			I-35
1-18			I-18	1-36			I-36

compound	core structure	Ar 1 and Ar 2	Ar 3	compound	core structure	Ar 1 and Ar 2	Ar 3
1-37	chemical formula 2-2	methyl group	I-1	1-55	chemical formula 2-2	methyl group	I-19
1-38			I-2	1-56			I-20
1-39			I-3	1-57			I-21
1-40			I-4	1-58			I-22
1-41			I-5	1-59			I-23
1-42			I-6	1-60			I-24
1-43			I-7	1-61			I-25
1-44			I-8	1-62			I-26
1-45			I-9	1-63			I-27
1-46			I-10	1-64			I-28
1-47			I-11	1-65			I-29
1-48			I-12	1-66			I-30
1-49			I-13	1-67			I-31
1-50			I-14	1-68			I-32
1-51			I-15	1-69			I-33
1-52			I-16	1-70			I-34
1-53			I-17	1-71			I-35
1-54			I-18	1-72			I-36

compound	core structure	Ar 1 and Ar 2	Ar 3	compound	core structure	Ar 1 and Ar 2	Ar 3
1-73	chemical formula 2-3	methyl group	I-1	1-91	chemical formula 2-3	methyl group	I-19
1-74			I-2	1-92			I-20
1-75			I-3	1-93			I-21
1-76			I-4	1-94			I-22
1-77			I-5	1-95			I-23
1-78			I-6	1-96			I-24
1-79			I-7	1-97			I-25
1-80			I-8	1-98			I-26
1-81			I-9	1-99			I-27
1-82			I-10	1-100			I-28
1-83			I-11	1-101			I-29
1-84			I-12	1-102			I-30
1-85			I-13	1-103			I-31
1-86			I-14	1-104			I-32
1-87			I-15	1-105			I-33
1-88			I-16	1-106			I-34
1-89			I-17	1-107			I-35
1-90			I-18	1-108			I-36

compound	core structure	Ar 1 and Ar 2	Ar 3	compound	core structure	Ar 1 and Ar 2	Ar 3
1-109	chemical formula 2-4	methyl group	I-1	1-127	chemical formula 2-4	methyl group	I-19
1-110			I-2	1-128			I-20
1-111			I-3	1-129			I-21
1-112			I-4	1-130			I-22
1-113			I-5	1-131			I-23
1-114			I-6	1-132			I-24
1-115			I-7	1-133			I-25
1-116			I-8	1-134			I-26
1-117			I-9	1-135			I-27
1-118			I-10	1-136			I-28
1-119			I-11	1-137			I-29
1-120			I-12	1-138			I-30
1-121			I-13	1-139			I-31
1-122			I-14	1-140			I-32
1-123			I-15	1-141			I-33
1-124			I-16	1-142			I-34
1-125			I-17	1-143			I-35
1-126			I-18	1-144			I-36

compound	core structure	Ar 1 and Ar 2	Ar 3	compound	core structure	Ar 1 and Ar 2	Ar 3
1-145	chemical formula 2-5	methyl group	I-1	1-163	chemical formula 2-5	methyl group	I-19
1-146			I-2	1-164			I-20
1-147			I-3	1-165			I-21
1-148			I-4	1-166			I-22
1-149			I-5	1-167			I-23
1-150			I-6	1-168			I-24
1-151			I-7	1-169			I-25
1-152			I-8	1-170			I-26
1-153			I-9	1-171			I-27
1-154			I-10	1-172			I-28
1-155			I-11	1-173			I-29
1-156			I-12	1-174			I-30
1-157			I-13	1-175			I-31
1-158			I-14	1-176			I-32
1-159			I-15	1-177			I-33
1-160			I-16	1-178			I-34
1-161			I-17	1-179			I-35
1-162			I-18	1-180			I-36

compound	core structure	Ar 1 and Ar 2	Ar 3	compound	core structure	Ar 1 and Ar 2	Ar 3
1-181	chemical formula 2-6	methyl group	I-1	1-199	chemical formula 2-6	methyl group	I-19
1-182			I-2	1-200			I-20
1-183			I-3	1-201			I-21
1-184			I-4	1-202			I-22
1-185			I-5	1-203			I-23
1-186			I-6	1-204			I-24
1-187			I-7	1-205			I-25
1-188			I-8	1-206			I-26
1-189			I-9	1-207			I-27
1-190			I-10	1-208			I-28
1-191			I-11	1-209			I-29
1-192			I-12	1-210			I-30
1-193			I-13	1-211			I-31
1-194			I-14	1-212			I-32
1-195			I-15	1-213			I-33
1-196			I-16	1-214			I-34
1-197			I-17	1-215			I-35
1-198			I-18	1-216			I-36

compound	core structure	Ar 1 and Ar 2	Ar 3	compound	core structure	Ar 1 and Ar 2	Ar 3
1-217	chemical formula 2-7	methyl group	I-1	1-235	chemical formula 2-7	methyl group	I-19
1-218			I-2	1-236			I-20
1-219			I-3	1-237			I-21
1-220			I-4	1-238			I-22
1-221			I-5	1-239			I-23
1-222			I-6	1-240			I-24
1-223			I-7	1-241			I-25
1-224			I-8	1-242			I-26
1-225			I-9	1-243			I-27
1-226			I-10	1-244			I-28
1-227			I-11	1-245			I-29
1-228			I-12	1-246			I-30
1-229			I-13	1-247			I-31
1-230			I-14	1-248			I-32
1-231			I-15	1-249			I-33
1-232			I-16	1-250			I-34
1-233			I-17	1-251			I-35
1-234			I-18	1-252			I-36

compound	core structure	Ar 1 and Ar 2	Ar 3	compound	core structure	Ar 1 and Ar 2	Ar 3
1-253	chemical formula 2-8	methyl group	I-1	1-271	chemical formula 2-8	methyl group	I-19
1-254			I-2	1-272			I-20
1-255			I-3	1-273			I-21
1-256			I-4	1-274			I-22
1-257			I-5	1-275			I-23
1-258			I-6	1-276			I-24
1-259			I-7	1-277			I-25
1-260			I-8	1-278			I-26
1-261			I-9	1-279			I-27
1-262			I-10	1-280			I-28
1-263			I-11	1-281			I-29
1-264			I-12	1-282			I-30
1-265			I-13	1-283			I-31
1-266			I-14	1-284			I-32
1-267			I-15	1-285			I-33
1-268			I-16	1-286			I-34
1-269			I-17	1-287			I-35
1-270			I-18	1-288			I-36

compound	core structure	Ar 1 and Ar 2	Ar 3	compound	core structure	Ar 1 and Ar 2	Ar 3
1-289	chemical formula 2-9	methyl group	I-1	1-307	chemical formula 2-9	methyl group	I-19
1-290			I-2	1-308			I-20
1-291			I-3	1-309			I-21
1-292			I-4	1-310			I-22
1-293			I-5	1-311			I-23
1-294			I-6	1-312			I-24
1-295			I-7	1-313			I-25
1-296			I-8	1-314			I-26
1-297			I-9	1-315			I-27
1-298			I-10	1-316			I-28
1-299			I-11	1-317			I-29
1-300			I-12	1-318			I-30
1-301			I-13	1-319			I-31
1-302			I-14	1-320			I-32
1-303			I-15	1-321			I-33
1-304			I-16	1-322			I-34
1-305			I-17	1-323			I-35
1-306			I-18	1-324			I-36

The organic optoelectronic device is not particularly limited as long as it is a device that can mutually convert electrical energy and light energy, and examples include organic photoelectric devices, organic light emitting devices, organic solar cells, and organic photoreceptor drums.

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

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

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

The anode 120 may be made of a conductor with a high work function to facilitate hole injection, for example, and may be made of metal, metal oxide, and/or conductive polymer. The anode 120 is made of metals such as nickel, platinum, vanadium, chromium, copper, zinc, gold, or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); Combinations of metals and oxides such as ZnO and Al or SnO ₂ and Sb; Conductive polymers such as poly(3-methylthiophene), poly(3,4-(ethylene-1,2-dioxy)thiophene) (polyehtylenedioxythiophene: PEDOT), polypyrrole, and polyaniline may be included, but are limited thereto. That is not the case.

The cathode 110 may be made of a conductor with a low work function to facilitate electron injection, for example, and may be made of metal, metal oxide, and/or conductive polymer. The cathode 110 is, for example, a metal such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, lead, cesium, barium, or an alloy thereof; Multilayer structure materials such as LiF/Al, LiO ₂ /Al, LiF/Ca, LiF/Al, and BaF ₂ /Ca may be included, but are not limited thereto.

The organic layer 105 includes a light-emitting layer 130, and the light-emitting layer 130 may include a known host and a known dopant.

The host is a known host material and may be a single compound or a mixture of two or more known host materials, and may be included at a weight ratio of, for example, 1:99 to 99:1.

Within the above range, it may be included in a weight ratio of, for example, about 10:90 to 90:10, about 20:80 to 80:20, for example, about 20:80 to about 70:30, about 20:80 to about 60:40, And it may be included in a weight ratio of about 30:70 to about 60:40. As a specific example, it may be included in a weight ratio of 40:60, 50:50, or 60:40.

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

A dopant is a substance that emits light when mixed in a small amount in a compound or composition for an organic optoelectronic device. Generally, a material such as a metal complex that emits light by multiple excitation that excites the triplet state or higher is used. You can. The dopant may be, for example, an inorganic, organic, or organic/inorganic compound, and may be included in one or two or more types.

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

The organic layer may further include a charge transport region in addition to the light emitting layer.

The charge transport region may be, for example, a hole transport region 140.

The hole transport region 140 can further increase hole injection and/or hole mobility between the anode 120 and the light emitting layer 130 and block electrons.

The hole transport region 140 may include the above-described compound for organic optoelectronic devices.

Specifically, the hole transport region 140 may include a hole transport layer between the anode 120 and the light-emitting layer 130, and a hole transport auxiliary layer between the light-emitting layer 130 and the hole transport layer, and the hole transport auxiliary layer. The layer may include the compounds for organic optoelectronic devices described above.

Additionally, the charge transport region may be, for example, an electron transport region 150.

The electron transport region 150 can further increase electron injection and/or electron mobility between the cathode 110 and the light emitting layer 130 and block holes.

Specifically, the electron transport region 150 may include an electron transport layer between the cathode 110 and the light-emitting layer 130, and an electron transport auxiliary layer between the light-emitting layer 130 and the electron transport layer, and is included in group A below. At least one of the listed compounds may be included in at least one of the electron transport layer and the electron transport auxiliary layer.

[Group A]

One embodiment may be an organic light-emitting device including a light-emitting layer as an organic layer.

Another embodiment may be an organic light-emitting device including a light-emitting layer and a hole transport region as the organic layer.

Another embodiment may be an organic light-emitting device including a light-emitting layer and an electron transport region as the organic layer.

As shown in FIG. 1 , the organic light emitting device according to an embodiment of the present invention may include an organic layer 105 and a hole transport region 140 and an electron transport region 105 in addition to the light emitting layer 130 .

Meanwhile, the organic light emitting device may further include an electron injection layer (not shown), a hole injection layer (not shown), etc. in addition to the light emitting layer as the organic layer described above.

The organic light emitting device 100 forms an anode or a cathode on a substrate, forms an organic layer using a dry film deposition method such as vacuum evaporation, sputtering, plasma plating, or ion plating, and then forms a cathode or cathode on the organic layer. It can be manufactured by forming an anode.

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

The above-described implementation example will be described in more detail through examples below. However, the following examples are for illustrative purposes only and do not limit the scope of rights.

Hereinafter, starting materials and reactants used in the examples and synthesis examples were purchased from Sigma-Aldrich, TCI, Tokyo Chemical Industries, or synthesized through known methods, unless otherwise specified.

(Manufacture of compounds for organic optoelectronic devices)

Synthesis Example 1: Synthesis of Compound 1-40

[Scheme 1]

7.6g (31 mmol) of 3-chloro-5,5-dimethyl-5H-dibenzo[b,d]silole (CAS No.: 1252259-63-4), N-(3-(9-phenyl) in a round bottom flask -9H-fluoren-9-yl)phenyl)-[1,1'-biphenyl]-4-amine (CAS No.: 2305719-96-2) 15g (31 mmol), Tris(dibenzylideneacetone)dipalladium(0) 1.4 g (1.5 mmol), 0.94 g (4.6 mmol) of Tri-tert-butylphosphine, 4.5 g (46 mmol) of Sodium tert-butoxide, and 90 mL of toluene were added and heated to reflux under a nitrogen atmosphere. After 6 hours, the reaction solution is cooled and extracted with water and ethyl acetate. The organic layer is dried under reduced pressure. The obtained solid is column purified using methylene chloride and n-hexane as mobile phases. The obtained solution was dried under reduced pressure to obtain 16 g (74.7% yield) of compound 1-40. (LC/MS[+H] = 694.63)

Synthesis Example 2: Synthesis of Compound 1-76

[Scheme 2]

10g (34.6 mmol) of 3-chloro-5,5-dimethyl-5H-dibenzo[b,d]silole (CAS No.: 1252259-63-4), N-(4-(9-phenyl-) in a round bottom flask 9H-fluoren-9-yl)phenyl)-[1,1'-biphenyl]-4-amine (CAS No.: 1853122-02-7) 16.8g (34.6 mmol), Tris(dibenzylideneacetone)dipalladium(0) 1.58 g (1.7 mmol), 1.05 g (5.2 mmol) of Tri-tert-butylphosphine, 5 g (51.9 mmol) of Sodium tert-butoxide, and 100 mL of toluene were added and heated to reflux under a nitrogen atmosphere. After 6 hours, the reaction solution is cooled and extracted with water and ethyl acetate. The organic layer is dried under reduced pressure. The obtained solid is column purified using methylene chloride and n-hexane as mobile phases. The obtained solution was dried under reduced pressure to obtain 15 g (63% yield) of compound 1-76. (LC/MS[+H] = 694.63)

Synthesis Example 3: Synthesis of Compound 1-292

[Scheme 3]

Step 1: Synthesis of Int-1

30 g (93.3 mmol) of N-([1,1'-biphenyl]-4-yl)-[1,1'-biphenyl]-2-amine (CAS No.: 1372775-52-4) in a round bottom flask, Add 24.1g (93.3 mmol) of 9-phenyl-9H-fluoren-9-ol (CAS No.: 25603-67-2), 19.9g (140 mmol) of boron trifluoride diethyl etherate and 100 mL of methylenechloride and leave under nitrogen atmosphere for 12 hours. Stir at room temperature. After completing the reaction by adding excess water, extract with methylenechloride. The organic layer was dried under reduced pressure to obtain 34 g (65% yield) of Int-1. (LC/MS[+H] = 563.00)

Step 2: Synthesis of Compound 1-292

8.7g (35.6 mmol) of 3-chloro-5,5-dimethyl-5H-dibenzo[b,d]silole (CAS No.: 1252259-63-4), 20g (35.6 mmol) of Int-1, in a round bottom flask. Add 1.6g (1.8 mmol) of Tris(dibenzylideneacetone)dipalladium(0), 0.72g (3.6 mmol) of Tri-tert-butylphosphine, 4.5g (46.3 mmol) of Sodium tert-butoxide, and 100 mL of toluene and heat to reflux under nitrogen atmosphere. After 6 hours, the reaction solution is cooled and extracted with water and ethyl acetate. The organic layer is dried under reduced pressure. The obtained solid is column purified using methylene chloride and n-hexane as mobile phases. The obtained solution was dried under reduced pressure to obtain 17 g (69% yield) of compound 1-292. (LC/MS[+H] = 694.63)

Synthesis Example 4: Synthesis of Compound 1-51

[Scheme 4]

Step 1: Synthesis of Int-2

10g (40.5 mmol) of 1-bromodibenzo[b,d]furan (CAS No.: 50548-45-3), 3-(9-phenyl-9H-fluoren-9-yl)aniline (CAS No.: 50548-45-3) was added to a round bottom flask. : 2452270-61-8) 17.5g (52.6 mmol), Tris(dibenzylideneacetone)dipalladium(0) 2.22g (2.4 mmol), Tri-tert-butylphosphine 2.95g (7.3 mmol), Sodium tert-butoxide 5g (53 mmol) Add 120 mL of toluene and heat to reflux under nitrogen atmosphere. After 6 hours, the reaction solution is cooled and extracted with water and ethyl acetate. The organic layer is dried under reduced pressure. The obtained solid is column purified using methylene chloride and n-hexane as mobile phases. The obtained solution was dried under reduced pressure to obtain 18 g (89% yield) of Int-2. (LC/MS[+H] = 500.47)

Step 2: Synthesis of Compound 1-51

In a round bottom flask, 8.8g (36 mmol) of 3-chloro-5,5-dimethyl-5H-dibenzo[b,d]silole (CAS No.: 1252259-63-4), 18g (36 mmol) of Int-2, Add 1g (1.1 mmol) of Tris(dibenzylideneacetone)dipalladium(0), 0.44g (2.2 mmol) of Tri-tert-butylphosphine, 4.5g (47 mmol) of Sodium tert-butoxide, and 100 mL of toluene, and heat and reflux under a nitrogen atmosphere. After 6 hours, the reaction solution is cooled and extracted with water and ethyl acetate. The organic layer is dried under reduced pressure. The obtained solid is column purified using methylene chloride and n-hexane as mobile phases. The obtained solution was dried under reduced pressure to obtain 16 g (63% yield) of compound 1-51. (LC/MS[+H] = 708.59)

Synthesis Example 5: Synthesis of Compound 1-87

[Scheme 5]

Step 1: Synthesis of Int-3

11g (44.5 mmol) of 1-bromodibenzo[b,d]furan (CAS No.: 50548-45-3), 4-(9-phenyl-9H-fluoren-9-yl)aniline (CAS No.: 50548-45-3) were added to a round bottom flask. : 851343-45-8) 20.78g (62.3 mmol), Tris(dibenzylideneacetone)dipalladium(0) 2.45g (2.7 mmol), Tri-tert-butylphosphine 3.24g (8 mmol), Sodium tert-butoxide 5.6g (58 mmol) ) and 130 mL of toluene and heat to reflux under nitrogen atmosphere. After 6 hours, the reaction solution is cooled and extracted with water and ethyl acetate. The organic layer is dried under reduced pressure. The obtained solid is column purified using methylene chloride and n-hexane as mobile phases. The obtained solution was dried under reduced pressure to obtain 19 g (85% yield) of Int-3. (LC/MS[+H] = 500.50)

Step 2: Synthesis of Compound 1-87

9.15g (37.4 mmol) of 3-chloro-5,5-dimethyl-5H-dibenzo[b,d]silole (CAS No.: 1252259-63-4), 18.7g (37.4 mmol) of Int-3 in a round bottom flask. , Tris(dibenzylideneacetone)dipalladium(0) 1g (1.1 mmol), Tri-tert-butylphosphine 0.44g (2.2 mmol), Sodium tert-butoxide 4.5g (47 mmol) and toluene 100 mL were added and heated to reflux under nitrogen atmosphere. After 6 hours, the reaction solution is cooled and extracted with water and ethyl acetate. The organic layer is dried under reduced pressure. The obtained solid is column purified using methylene chloride and n-hexane as mobile phases. The obtained solution was dried under reduced pressure to obtain 18 g (68% yield) of compound 1-87. (LC/MS[+H] = 708.56)

Comparative Synthesis Example 1: Synthesis of Compound C-1

[Scheme 6]

10g (34.6 mmol) of 2-chloro-5,5-dimethyl-5H-dibenzo[b,d]silole (CAS No.: 1801753-03-6), N-(4-(9-phenyl-) in a round bottom flask 9H-fluoren-9-yl)phenyl)-[1,1'-biphenyl]-4-amine (CAS No.: 1853122-02-7) 16.8g (34.6 mmol), Tris(dibenzylideneacetone)dipalladium(0) 1.58 g (1.7 mmol), 1.05 g (5.2 mmol) of Tri-tert-butylphosphine, 5 g (51.9 mmol) of Sodium tert-butoxide, and 100 mL of toluene were added and heated to reflux under a nitrogen atmosphere. After 6 hours, the reaction solution is cooled and extracted with water and ethyl acetate. The organic layer is dried under reduced pressure. The obtained solid is column purified using methylene chloride and n-hexane as mobile phases. The obtained solution was dried under reduced pressure to obtain 14 g of compound C-1 (59% yield).

(Production of organic light-emitting devices)

Example 1

A glass substrate coated with a thin film of ITO (indium tin oxide) was ultrasonically cleaned with distilled water. After washing with distilled water, the substrate was ultrasonic cleaned with solvents such as isopropyl alcohol, acetone, and methanol, dried, and then transferred to a plasma cleaner. The substrate was cleaned for 10 minutes using oxygen plasma and then transferred to a vacuum evaporator. Using the prepared ITO transparent electrode as an anode, Compound A doped with 3% NDP-9 (commercially available from Novaled) was vacuum deposited on the ITO substrate to form a hole injection layer with a thickness of 100 Å, and the hole injection layer Compound A was deposited to a thickness of 1300 Å on top to form a hole transport layer. Compound 1-40 obtained in Synthesis Example 1 was deposited on the top of the hole transport layer to a thickness of 320 Å to form a hole transport auxiliary layer, and a first host and a second host were used simultaneously on the top of the hole transport auxiliary layer, and GD was used as a dopant. was doped at 10 wt% and a 330 Å thick light emitting layer was formed by vacuum deposition. Next, Compound B was deposited on top of the light emitting layer to a thickness of 50 Å to form an electron transport auxiliary layer, and Compound C and LiQ were simultaneously vacuum deposited at a weight ratio of 1:1 to form an electron transport layer with a thickness of 300 Å. An organic light emitting device was manufactured by sequentially vacuum depositing 15 Å of LiQ and 1,200 Å of Al on top of the electron transport layer to form a cathode.

ITO/Compound A (3% NDP-9 doping, 100Å)/ Compound A (1300Å)/ Compound 1-40 (320Å)/ EML [Host (1st host: 2nd host = 35:65): GD = 90 wt %:10wt%](330Å)/Compound B (50Å)/Compound C:LiQ(300Å)/LiQ(15Å)/Al(1200Å).

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

Compound B: 2-{3-[3-(9,9-dimethyl-9H-fluoren-2-l)phenyl]phenyl}-4,6-diphenyl-1,3,5-triazine

Compound C: 4-(4-{4-[4-(diphenyl-1,3,5-triazin-2-yl)phenyl]naphthalene-1-yl}phenyl)benzonitrile

[1st host] [2nd host] [GD]

Examples 2 to 5, and Comparative Example 1

An organic light emitting device was manufactured in the same manner as Example 1, except that the hole transport auxiliary layer was changed as shown in Table 10 below.

evaluation

The lifespan characteristics of organic light emitting devices according to Examples 1 to 5 and Comparative Example 1 were evaluated.

Examples 1 to 5 and Comparative Example 1 emit initial luminance (cd/m ² ) of 24,000 cd/m ² using a Polaronics life measurement system for the manufactured organic light emitting device, and the luminance decreases over time. was measured, and the point at which the luminance was reduced to 97% of the initial luminance was measured as T97 lifespan.

Relative values based on the T97 lifespan of Comparative Example 1 were calculated and shown in Table 10 below.

division	Hole transport auxiliary layer	T97 life (%)
Example 1	1-40	135
Example 2	1-51	160
Example 3	1-76	143
Example 4	1-87	160
Example 5	1-292	140
Comparative Example 1	C-1	100

Referring to Table 10, it can be seen that the lifespan of the compound according to the present invention is significantly improved compared to the comparative compound.

Although the embodiments have been described in detail, the scope of the present invention is not limited thereto, and various modifications and improvements made by those skilled in the art using the basic concept of the present invention defined in the following claims also fall within the scope of the present invention. will be.

Claims (10)

1. Compound for organic optoelectronic devices represented by the following formula (1):

   [Formula 1]

   

   In Formula 1,

   Ar ¹ and Ar ² are each independently a substituted or unsubstituted C1 to C10 alkyl group or a substituted or unsubstituted C6 to C20 aryl group,

   Ar ³ is a substituted or unsubstituted C6 to C30 aryl group or a substituted or unsubstituted C2 to C30 heterocyclic group,

   R ¹ to R ⁶ are each independently hydrogen, deuterium, halogen group, cyano group, substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C6 to C30 aryl group, or substituted or unsubstituted C6 to C30 heterocycle. It is a spirit,

   n1, n3, n5 and n6 are each independently an integer from 1 to 4,

   n2 is one of the integers from 1 to 3,

   n4 is one of the integers from 1 to 5.
2. In paragraph 1:

   Formula 1 is a compound for an organic optoelectronic device represented by any one of the following Formulas 1-I to 1-III:

   [Formula 1-Ⅰ] [Formula 1-Ⅱ] [Formula 1-Ⅲ]

   

   In Formula 1-I to Formula 1-III,

   Ar ¹ to Ar ³ , R ¹ to R ⁶ , and n1 to n6 are as defined in claim 1.
3. In paragraph 1:

   Formula 1 is a compound for an organic optoelectronic device represented by any one of the following Formulas 1-1 to 1-6:

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

   

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

   

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

   

   In Formulas 1-1 to 1-6,

   Ar ¹ to Ar ³ , R ¹ to R ⁶ , and n2 to n6 are as defined in claim 1,

   n1', n3', n5', and n6' are each independently integers of 1 or 2.
4. In paragraph 1:

   Ar ³ is 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, or a substituted or unsubstituted phenane. Trenyl group, substituted or unsubstituted chrysenyl group, substituted or unsubstituted fluorenyl group, substituted or unsubstituted triphenylene group, substituted or unsubstituted dibenzofuranyl group, substituted or unsubstituted dibenzothiophenyl group Or a substituted or unsubstituted dibenzosilolyl group, a compound for an organic optoelectronic device.
5. In paragraph 1:

   A compound for an organic optoelectronic device, wherein Ar ³ is one selected from the substituents listed in Group I below:

   [Group Ⅰ]

   

   

   

   .
6. According to paragraph 1,

   Ar ¹ and Ar ² are each independently a substituted or unsubstituted C1 to C5 alkyl group or a substituted or unsubstituted C6 to C12 aryl group.
7. According to paragraph 1,

   A compound for an organic optoelectronic device selected from the compounds listed in Group 1 below:

   [Group 1]

   

   

   

   

   

   

   

   

   

   .
8. Anode and cathode facing each other,

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

   The organic layer is an organic optoelectronic device comprising the compound for an organic optoelectronic device according to any one of claims 1 to 7.
9. According to clause 8,

   The organic layer is a light emitting layer, and

   Comprising a hole transport region between the anode and the light emitting layer,

   The hole transport region is an organic optoelectronic device comprising the compound for an organic optoelectronic device.
10. A display device comprising the organic optoelectronic device according to claim 8.

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