KR20220062989A - Organic optoelectronic device and display device - Google Patents

Abstract

The present invention relates to an organic optoelectronic device and a display device. The organic optoelectronic device comprises: a positive electrode and negative electrode facing each other; a light emitting layer positioned between the positive electrode and the negative electrode; a hole transport layer positioned between the positive electrode and the light emitting layer; and a hole transport auxiliary layer positioned between the light emitting layer and the hole transport layer. The light emitting layer includes a first compound represented by a combination of chemical formulas 1 and 2 and a second compound represented by a chemical formula 3. The hole transport auxiliary layer includes a third compound represented by a combination of formulas 4 and 5. The content of chemical formulas 1 to 5 are as defined in the specification.

Description

Organic optoelectronic device and display device {ORGANIC OPTOELECTRONIC DEVICE AND DISPLAY DEVICE}

It relates to an organic optoelectronic device and a display device.

An organic optoelectronic diode is a device capable of converting electrical energy and optical energy.

Organic optoelectronic devices can be roughly divided into two types according to their operating principles. One is a photoelectric device that generates electrical energy as excitons formed by light energy are separated into electrons and holes, and electrons and holes are transferred to different electrodes, and the other is electrical energy by supplying voltage or current to the electrode. It is a light emitting device that generates light energy from

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

Among them, organic light emitting diodes (OLEDs) have recently received a lot of attention due to an increase in demand for flat panel display devices. The organic light emitting device is a device that converts electrical energy into light, and the performance of the organic light emitting device is greatly affected by an organic material positioned between electrodes.

One embodiment provides a high efficiency, long life and low driving organic optoelectronic device.

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

According to one embodiment, an anode and a cathode facing each other, a light emitting layer positioned between the anode and the cathode, a hole transport layer positioned between the anode and the light emitting layer, and a hole transport aid positioned between the light emitting layer and the hole transport layer a layer, wherein the light emitting layer includes a first compound represented by a combination of Formula 1 and Formula 2 and a second compound represented by Formula 3 below, and the hole transport auxiliary layer includes Formula 4 and Formula 5 below. It provides an organic optoelectronic device comprising a third compound represented by a combination of.

[Formula 1] [Formula 2]

In Formula 1 and Formula 2,

L ¹ to L ³ are each independently a single bond, a substituted or unsubstituted C6 to C20 arylene group, or a substituted or unsubstituted C2 to C20 heterocyclic group,

Ar ¹ and Ar ² are each independently a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heterocyclic group,

X ¹ is O or S,

a ₁ * to a ₄ * are each independently a linking carbon (C) or CR ^a ,

Adjacent two of a ₁ * to a ₄ * of Formula 1 are each connected to Formula 2,

* is the connection point,

R ^a and R ¹ to R ⁸ are each independently hydrogen, deuterium, a cyano group, a halogen 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;

[Formula 3]

In Formula 2,

Ar ³ and Ar ⁴ are each independently a substituted or unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted C2 to C30 heterocyclic group,

L ⁴ and L ⁵ are each independently a single bond, or a substituted or unsubstituted C6 to C20 arylene group,

R ^b and R ⁹ to R ¹⁸ are each independently hydrogen, deuterium, a cyano group, a halogen group, a substituted or unsubstituted amine group, a substituted or unsubstituted C1 to C30 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group , or a substituted or unsubstituted C2 to C30 heterocyclic group,

m is an integer from 0 to 2;

[Formula 4] [Formula 5]

In Chemical Formulas 4 and 5,

Y ¹ and Y ² are each independently a substituted or unsubstituted C1 to C30 alkyl group or a substituted or unsubstituted C6 to C30 aryl group,

X ² is O or S,

b ₁ * to b ₄ * are each independently a linking carbon (C) or CR ^c ,

Two adjacent ones of b ₁ * to b ₄ * of Formula 4 are each connected to Formula 5,

* is the connection point,

R ^c and R ¹⁹ to R ²³ are each independently hydrogen, deuterium, cyano group, halogen group, substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C6 to C30 aryl group, or substituted or unsubstituted C2 to C30 heterocyclic group,

L ⁶ To L ⁸ are each independently a single bond, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heterocyclic group, or a combination thereof,

Ar ⁵ and Ar ⁶ are each independently a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heterocyclic group.

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

It is possible to realize an organic optoelectronic device with low driving, high efficiency and long life.

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

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

As used herein, unless otherwise defined, at least one hydrogen in a substituent or compound is deuterium, a halogen group, a hydroxyl group, an amino group, a substituted or unsubstituted C1 to C30 amine group, a nitro group, a 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, a C1 to C20 alkoxy group, a C1 to C10 trifluoroalkyl group, a cyano group, or a combination thereof.

In one embodiment of the present invention, "substitution" means that at least one hydrogen in a substituent or compound is deuterium, a C1 to C30 alkyl group, a C1 to C10 alkylsilyl group, a C6 to C30 arylsilyl group, a C3 to C30 cycloalkyl group, and a 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. In addition, in a specific embodiment of the present invention, "substitution" means that at least one hydrogen in a substituent or compound is substituted with deuterium, a C1 to C20 alkyl group, a C6 to C30 aryl group, or a cyano group. In addition, in a specific example of the present invention, "substitution" means that at least one hydrogen in a substituent or compound is substituted 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 that at least one hydrogen in a substituent or compound is substituted with deuterium, a cyano group, a methyl group, an ethyl group, a propyl group, a butyl group, a phenyl group, a biphenyl group, a terphenyl group or a naphthyl group means it has been

In the present specification, "hetero" means that, unless otherwise defined, 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. .

As used herein, the term "aryl group" is a concept that encompasses a group having one or more hydrocarbon aromatic moieties, and all elements of the hydrocarbon aromatic moiety have p-orbitals, and these p-orbitals are conjugated. It contains a form that forms, for example, a phenyl group, a naphthyl group, etc., and 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 quaterphenyl group, etc., and two or more hydrocarbon aromatic moieties They may include a non-aromatic fused ring fused directly or indirectly, such as a fluorenyl group, and the like.

Aryl groups include monocyclic, polycyclic or fused ring polycyclic (ie, rings bearing adjacent pairs of carbon atoms) functional groups.

In the present specification, "heterocyclic group" is a higher concept including a heteroaryl group, and instead of carbon (C) in a ring compound such as an aryl group, a cycloalkyl group, a fused ring thereof, or a combination thereof, N, O, 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 include one or more heteroatoms.

For example, "heteroaryl group" means containing at least one hetero atom selected from the group consisting of N, O, S, P and Si in the aryl group. 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 include 1 to 3 heteroatoms.

More specifically, a 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 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 triphenylene group, substituted or unsubstituted perylenyl group, substituted or unsubstituted fluorenyl group, substituted or unsubstituted indenyl group, substituted or unsubstituted It may be a cyclic furanyl group, or a combination thereof, but is not limited thereto.

More specifically, a substituted or unsubstituted C2 to C30 heterocyclic group includes 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 A substituted or unsubstituted pyrimidinyl group, a substituted or unsubstituted pyrazinyl group, a substituted or unsubstituted triazinyl group, a substituted or unsubstituted benzofuranyl group, a substituted or unsubstituted benzothiophenyl group, A substituted or unsubstituted benzimidazolyl group, a substituted or unsubstituted indolyl group, a substituted or unsubstituted quinolinyl group, a substituted or unsubstituted isoquinolinyl group, a substituted or unsubstituted quinazolinyl group, a substituted or unsubstituted quinoxalinyl group, substituted or unsubstituted naphthyridinyl group, substituted or unsubstituted benzofuranpyrimidinyl group, substituted or unsubstituted benzothiophenepyrimidinyl group, substituted or unsubstituted benzoxazinyl group, substituted or unsubstituted A substituted benzthiazinyl 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 carba It may be a zolyl group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted dibenzothiophenyl group, or a combination thereof, but is not limited thereto.

As used herein, the hole property refers to a property capable of forming a hole by donating electrons when an electric field is applied. It refers to a characteristic that facilitates the movement of holes formed in the anode and in the light emitting layer.

In addition, the electronic property refers to a property that can receive electrons when an electric field is applied. It has conduction properties along the LUMO level, so electrons formed in the cathode are injected into the light emitting layer, electrons formed in the light emitting layer are moved to the cathode, and in the light emitting layer. It refers to a characteristic that facilitates movement.

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

The organic optoelectronic device is not particularly limited as long as it is a device capable of converting electrical energy and optical energy, and examples thereof include an organic photoelectric device, an organic light emitting device, an organic solar cell, and an organic photosensitive drum.

Herein, an organic light emitting device, which is an example of an organic optoelectronic device, will be described as an example, but the present invention is not limited thereto and may be equally applied to other organic optoelectronic devices.

In order to clearly express various layers and regions in the drawings, the thicknesses are enlarged. Throughout the specification, like reference numerals are assigned to similar parts. When a part, such as a layer, film, region, plate, etc., is said to be “on” another part, it includes not only cases where it is “directly on” another part, but also cases where there is another part in between. Conversely, when we say that a part is "just above" another part, we mean that there is no other part in the middle.

1 is a cross-sectional view schematically illustrating an organic light emitting diode according to an exemplary embodiment.

Referring to FIG. 1 , an organic light emitting diode 300 according to an embodiment includes an anode 110 and a cathode 120 facing each other, and an organic layer 105 positioned between the anode 110 and the cathode 120 . and the organic layer 105 includes a light emitting layer 130 , a hole transport auxiliary layer 142 , and a hole transport layer 141 .

The anode 110 may be made of, for example, a conductor having a high work function to facilitate hole injection, and may be made of, for example, a metal, a metal oxide, and/or a conductive polymer. The anode 110 may include, for example, a metal such as nickel, platinum, vanadium, chromium, copper, zinc, gold, or an alloy thereof; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); 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, but are limited thereto it is not

The cathode 120 may be made of, for example, a conductor having a low work function to facilitate electron injection, and may be made of, for example, a metal, a metal oxide, and/or a conductive polymer. The negative electrode 120 may include, 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; and a multilayer structure material such as LiF/Al, LiO ₂ /Al, LiF/Ca, LiF/Al, and BaF ₂ /Ca, but is not limited thereto.

The emission layer 130 is positioned between the anode 110 and the cathode 120 , and includes a plurality of hosts and at least one kind of dopant.

The emission layer 130 may include, as a host, a first compound having relatively strong hole characteristics and a second compound having relatively strong electron characteristics.

The first compound is a compound having relatively strong electronic properties, and may be represented by a combination of Chemical Formulas 1 and 2 below.

[Formula 1] [Formula 2]

In Formula 1 and Formula 2,

L ¹ to L ³ are each independently a single bond, a substituted or unsubstituted C6 to C20 arylene group, or a substituted or unsubstituted C2 to C20 heterocyclic group,

Ar ¹ and Ar ² are each independently a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heterocyclic group,

X ¹ is O or S,

a ₁ * to a ₄ * are each independently a linking carbon (C) or CR ^a ,

Adjacent two of a ₁ * to a ₄ * of Formula 1 are each connected to Formula 2,

* is the connection point,

R ^a and R ¹ to R ⁸ are each independently hydrogen, deuterium, a cyano group, a halogen 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.

The first compound is a form in which a substituted or unsubstituted triazine is substituted with benzofurancarbazole or benzothiophenecarbazole, and as benzofuran or benzothiophene is fused to a carbazole moiety, it expands the HOMO electron cloud to facilitate hole injection and transmission characteristics. In the case of an organic light emitting device to which this is applied, the driving voltage of the device may be lowered, and lifespan characteristics may be improved due to stability due to hole and electron balance.

In particular, as the triazine is substituted in the N-direction of the carbazole moiety, electrons and holes are well separated in the molecule, thereby further improving charge injection and transfer properties.

On the other hand, it is included together with the second compound to exhibit good interfacial properties and hole and electron transport ability, thereby lowering the driving voltage of a device to which it is applied.

For example, L ² and L ³ are each independently a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted dibenzofuranylene group, a substituted or unsubstituted dibenzothiophenylene group, or a substituted or unsubstituted It may be a cyclic carbazolylene group.

For example, L ² and L ³ may each independently be a single bond, a substituted or unsubstituted phenylene group, or a substituted or unsubstituted carbazolylene group.

For example, Ar ¹ and Ar ² are each independently a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, or It may be a substituted or unsubstituted carbazolyl group.

As a specific example, Ar ¹ and Ar ² may be unsubstituted or substituted with a phenyl group.

For example, Ar ¹ and Ar ² may each independently represent a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, or a substituted or unsubstituted carbazolyl group.

In an embodiment, L ² -Ar ¹ and L ³ -Ar ² may each independently be selected from the substituents listed in Group I below.

[Group I]

In the above group I, * is a connection point.

For example, L ¹ may be a single bond or a substituted or unsubstituted phenylene group.

For example, L ¹ may be a single bond.

For example, R ^a and R ¹ to R ⁸ may each independently be hydrogen or a substituted or unsubstituted phenyl group.

As a specific example, any one of R ^a , R ⁵ , R ⁶ and R ⁸ may be a substituted or unsubstituted phenyl group, and the remainder may be hydrogen.

For example, R ^a and R ¹ to R ⁸ may each be hydrogen.

As an example, the first compound may be, for example, represented by any one of the following Chemical Formulas 1A to 1F depending on the fusion position of Chemical Formulas 1 and 2.

[Formula 1A] [Formula 1B]

[Formula 1C] [Formula 1D]

[Formula 1E] [Formula 1F]

In Formula 1A to Formula 1F,

L ¹ to L ³ , Ar ¹ , Ar ² , X ¹ and R ¹ to R ⁸ are the same as described above, and R ^a1 to R ^a4 are each independently the same as defined for R ^a described above.

As a specific example, the first compound may be represented by any one of Formula 1A, Formula 1B, Formula 1C, Formula 1D, and Formula 1F.

As a more specific example, the first compound may be represented by Formula 1A or Formula 1C.

The first compound may be, for example, one selected from the compounds listed in Group 1, but is not limited thereto.

[Group 1]

[1-1] [1-2] [1-3] [1-4]

[1-5] [1-6] [1-7] [1-8]

[1-9] [1-10] [1-11] [1-12]

[1-13] [1-14] [1-15] [1-16]

[1-17] [1-18] [1-19] [1-20]

[1-21] [1-22] [1-23] [1-24]

[1-25] [1-26] [1-27] [1-28]

[1-29] [1-30] [1-31] [1-32]

[1-33] [1-34] [1-35] [1-36]

[1-37] [1-38] [1-39] [1-40]

[1-41] [1-42] [1-43] [1-44]

[1-45] [1-46] [1-47] [1-48]

[1-49] [1-50] [1-51] [1-52]

[1-53] [1-54] [1-55] [1-56]

[1-57] [1-58] [1-59] [1-60]

[1-61] [1-62] [1-63] [1-64]

[1-65] [1-66] [1-67] [1-68]

[1-69] [1-70] [1-71] [1-72]

[1-73] [1-74] [1-75] [1-76]

[1-77] [1-78] [1-79] [1-80]

[1-81] [1-82] [1-83] [1-84]

[1-85] [1-86] [1-87] [1-88]

[1-89] [1-90] [1-91] [1-92]

[1-93] [1-94] [1-95] [1-96]

[1-97] [1-98] [1-99] [1-100]

[1-101] [1-102] [1-103] [1-104]

[1-105] [1-106] [1-107] [1-108]

[1-109] [1-110] [1-111] [1-112]

[1-113] [1-114] [1-115] [1-116]

[1-117] [1-118] [1-119] [1-120]

[1-121] [1-122] [1-123] [1-124]

[1-125] [1-126] [1-127] [1-128]

[1-129] [1-130] [1-131] [1-132]

[1-133] [1-134] [1-135] [1-136]

[1-137] [1-138] [1-139] [1-140]

[1-141] [1-142] [1-143] [1-144]

[1-145] [1-146] [1-147] [1-148]

[1-149] [1-150] [1-151] [1-152]

[1-153] [1-154] [1-155] [1-156]

[1-157] [1-158] [1-159] [1-160]

[1-161] [1-162] [1-163] [1-164]

The second compound is a compound having a relatively strong hole property and may be represented by the following Chemical Formula 3.

[Formula 3]

In Formula 3,

Ar ³ and Ar ⁴ are each independently a substituted or unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted C2 to C30 heterocyclic group,

L ⁴ and L ⁵ are each independently a single bond, or a substituted or unsubstituted C6 to C20 arylene group,

R ^b and R ⁹ to R ¹⁸ are each independently hydrogen, deuterium, a cyano group, a halogen group, a substituted or unsubstituted amine group, a substituted or unsubstituted C1 to C30 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group , or a substituted or unsubstituted C2 to C30 heterocyclic group,

m is an integer from 0 to 2.

The second compound may be used in the light emitting layer together with the first compound to increase the mobility of charges and improve stability, thereby improving luminous efficiency and lifespan characteristics.

For example, Ar ³ and Ar ⁴ of Formula 3 are each 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, substituted or unsubstituted triphenylenyl group, substituted or unsubstituted carbazolyl group, substituted or unsubstituted dibenzothiophenyl group, substituted or unsubstituted dibenzofuranyl group, substituted or unsubstituted a substituted fluorenyl group, or a substituted or unsubstituted pyridinyl group,

In Formula 3, L ⁴ and L ⁵ are each independently a single bond, a substituted or unsubstituted phenylene group, or a substituted or unsubstituted biphenylene group,

In Formula 3, R ⁹ to R ¹⁸ are each independently hydrogen, deuterium, or a substituted or unsubstituted C6 to C12 aryl group,

m may be 0 or 1.

For example, “substitution” in Formula 3 means that at least one hydrogen is substituted with deuterium, a C1 to C4 alkyl group, a C6 to C18 aryl group, or a C2 to C30 heteroaryl group.

In a specific embodiment of the present invention, Chemical Formula 3 may be represented by one of Chemical Formulas 3-1 to 3-15 below.

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

[Formula 3-4] [Formula 3-5] [Formula 3-6]

[Formula 3-7] [Formula 3-8] [Formula 3-9]

[Formula 3-10] [Formula 3-11] [Formula 3-12]

[Formula 3-13] [Formula 3-14] [Formula 3-15]

In Formulas 3-1 to 3-15, R ⁹ to R ¹⁸ are each independently hydrogen or a substituted or unsubstituted C6 to C12 aryl group, *-L ⁴ -Ar ³ and *-L ⁵ -Ar ⁴ may each independently be one of the substituents listed in Group II below.

[Group II]

In the above group II, * is a connection point.

In an embodiment, Chemical Formula 3 may be represented by Chemical Formula 3-8.

In addition, *-L ⁴ -Ar ³ and *-L ⁵ -Ar ⁴ of Formula 3-8 may each independently be selected from Group II, for example, C-1, C-2, C-3 and C It may be any one of -19.

In the most specific embodiment, all of *-L ⁴ -Ar ³ and *-L ⁵ -Ar ⁴ may be represented by C-1, C-2, or C-3 of Group II, but is not limited thereto. .

In a specific embodiment of the present invention, the second compound may be represented by Formula 3-8, and Ar ³ and Ar ⁴ of Formula 3-8 are each independently a substituted or unsubstituted phenyl group, a substituted or unsubstituted a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted dibenzothiophenyl group, and L ⁴ and L ⁵ are each independently a single bond, or A substituted or unsubstituted C6 to C20 arylene group, R ⁹ to R ¹⁸ are each independently hydrogen, deuterium, a cyano group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted carbazole It may be a diyl group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted dibenzothiophenyl group.

For example, the second compound may be one selected from the compounds listed in Group 2 below, but is not limited thereto.

[Group 2]

[2-1] [2-2] [2-3] [2-4] [2-5]

[2-6] [2-7] [2-8] [2-9] [2-10]

[2-11] [2-12] [2-13] [2-14] [2-15]

[2-16] [2-17] [2-18] [2-19] [2-20]

[2-21] [2-22] [2-23] [2-24] [2-25]

[2-26] [2-27] [2-28] [2-29] [2-30]

[2-31] [2-32] [2-33] [2-34] [2-35]

[2-36] [2-37] [2-38] [2-39] [2-40]

[2-41] [2-42] [2-43] [2-44] [2-45]

[2-46] [2-47] [2-48] [2-49] [2-50]

[2-51] [2-52] [2-53] [2-54] [2-55]

[2-56] [2-57] [2-58] [2-59] [2-60]

[2-61] [2-62] [2-63] [2-64] [2-65]

[2-66] [2-67] [2-68] [2-69] [2-70]

[2-71] [2-72] [2-73] [2-74] [2-75]

[2-76] [2-77] [2-78] [2-79] [2-80]

[2-81] [2-82] [2-83] [2-84] [2-85]

[2-86] [2-87] [2-88] [2-89] [2-90]

[2-91] [2-92] [2-93] [2-94] [2-95]

[2-96] [2-97] [2-98] [2-99] [2-100]

[2-101] [2-102] [2-103] [2-104] [2-105]

[2-106] [2-107] [2-108] [2-109] [2-110]

[2-111] [2-112] [2-113] [2-114] [2-115]

[2-116] [2-117] [2-118] [2-119] [2-120]

[2-121] [2-122] [2-123] [2-124] [2-125]

[2-126] [2-127] [2-128] [2-129] [2-130]

[2-131] [2-132] [2-133] [2-134] [2-135]

[2-136] [2-137] [2-138] [2-139] [2-140]

[2-141] [2-142] [2-143] [2-144] [2-145] [2-146]

[2-147] [2-148] [2-149] [2-150] [2-151] [2-152]

The first compound and the second compound may be included in a weight ratio of, for example, 1:99 to 99:1. By being included in the above range, the efficiency and lifespan can be improved by matching an appropriate weight ratio using the hole transport ability of the first compound and the electron transport ability of the second compound to implement bipolar characteristics. within this range such as about 10:90 to 90:10, about 10:90 to 80:20, about 10:90 to 70:30, about 10:90 to 60:40 or about 10:90 to about 50:50 may be included in the weight ratio of For example, it may be included in a weight ratio of 20:80 to 50:50, for example, it may be included in a weight ratio of 30:70 or 40:60.

In an embodiment of the present invention, each of the first compound and the second compound may be included as a host of the emission layer, for example, a phosphorescent host.

The light emitting layer may further include one or more compounds in addition to the above-described host.

The emission layer 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 phosphorescent dopant.

The dopant is a material that is mixed with the above-mentioned host in a small amount to cause light emission, and in general, a material such as a metal complex which emits light by multiple excitation excitation to a triplet state or more may be used. The dopant may be, for example, an inorganic, organic, or organic-inorganic compound, and may include one or two or more types.

Examples of the dopant include 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 Chemical Formula Z, but is not limited thereto.

[Formula Z]

L ⁹ MX ³

In Formula Z, M is a metal, and L ⁹ and X ³ are the same as or different from each other and are ligands forming a complex with M.

M may be, for example, Ir, Pt, Os, Ti, Zr, Hf, Eu, Tb, Tm, Fe, Co, Ni, Ru, Rh, Pd or a combination thereof, and L ⁹ and X ³ are, for example, bi It may be a dentate ligand.

It may be positioned between the light emitting layer 130 and the hole transport layer 141 to be described later, and in particular may be positioned in contact with the light emitting layer 130 . Since the hole transport auxiliary layer 142 is positioned in contact with the light emitting layer 130 , it is possible to precisely control the mobility of holes at the interface between the light emitting layer 130 and the hole transport layer 141 . The hole transport auxiliary layer 142 may include a plurality of layers.

The hole transport auxiliary layer 142 may include, for example, a third compound represented by a combination of Chemical Formulas 4 and 5 below.

[Formula 4] [Formula 5]

In Formulas 4 and 5,

Y ¹ and Y ² are each independently a substituted or unsubstituted C1 to C30 alkyl group or a substituted or unsubstituted C6 to C30 aryl group,

X ² is O or S,

b ₁ * to b ₄ * are each independently a linking carbon (C) or CR ^c ,

Two adjacent ones of b ₁ * to b ₄ * of Formula 4 are each connected to Formula 5,

* is the connection point,

R ^c and R ¹⁹ to R ²³ are each independently hydrogen, deuterium, a cyano group, a halogen 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,

L ⁶ To L ⁸ are each independently a single bond, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heterocyclic group, or a combination thereof,

Ar ⁵ and Ar ⁶ are each independently a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heterocyclic group.

The third compound is a compound having a high HOMO energy level and may have good hole injection properties. Accordingly, the third compound is applied to the hole transport auxiliary layer 142 to effectively improve hole mobility at the interface between the light emitting layer 130 and the hole transport layer 141 , thereby effectively lowering the driving voltage of the organic optoelectronic device.

For example, L ⁷ and L ⁸ may each independently represent a single bond, a substituted or unsubstituted phenylene group, or a substituted or unsubstituted naphthylene group.

For example, L ⁷ and L ⁸ may each independently represent a single bond, or a substituted or unsubstituted phenylene group.

For example, Ar ⁵ and Ar ⁶ are each 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 anthra group Cenyl group, substituted or unsubstituted phenanthrenyl group, substituted or unsubstituted fluorenyl group, substituted or unsubstituted dibenzofuranyl group, substituted or unsubstituted dibenzothiophenyl group, or substituted or unsubstituted carbazole it could be a diary

For example, Ar ⁵ and Ar ⁶ may each independently represent a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, or a substituted or unsubstituted fluorenyl group.

In an embodiment, L ⁷ -Ar ⁵ and L ⁸ -Ar ⁶ may each independently be selected from the substituents listed in Group Ⅲ below.

[Group III]

In the above group III, * is a connection point.

For example, L ⁶ may be a single bond or a substituted or unsubstituted phenylene group.

For example, Y ¹ and Y ² may each independently represent a substituted or unsubstituted C1 to C5 alkyl group or a substituted or unsubstituted C6 to C12 aryl group.

For example, Y ¹ and Y ² may each independently be an unsubstituted methyl group or an unsubstituted phenyl group.

For example, R ^c and R ¹⁹ to R ²³ may each independently represent hydrogen, a substituted or unsubstituted C1 to C5 alkyl group, or a substituted or unsubstituted C6 to C12 aryl group.

For example, R ^c and R ¹⁹ to R ²³ may each be hydrogen.

For example, the third compound may be, for example, represented by any one of the following Chemical Formulas 4A to 4F depending on the fusion position of Chemical Formulas 4 and 5.

[Formula 4A] [Formula 4B]

[Formula 4C] [Formula 4D]

[Formula 4E] [Formula 4F]

In Formulas 4A to 4F,

Y ¹ , Y ² , X ² , R ¹⁹ to R ²³ , L ⁶ to L ⁸ , Ar ⁵ and Ar ⁶ are the same as described above, and R ^c1 to R ^c4 are each independently the same as defined for R ^c .

Formula 4A may be, for example, represented by any one of the following Formulas 4A-1 to 4A-4 depending on the specific substitution position of the amine group.

[Formula 4A-1] [Formula 4A-2]

[Formula 4A-3] [Formula 4A-4]

In Formulas 4A-1 to 4A-4, Y ¹ , Y ² , X ² , R ¹⁹ to R ²³ , L ⁶ to L ⁸ , Ar ⁵ , Ar ⁶ , R ^c3 and R ^c4 are the same as described above.

Formula 4B may be, for example, represented by any one of the following Formulas 4B-1 to 4B-4 depending on the specific substitution position of the amine group.

[Formula 4B-1] [Formula 4B-2]

[Formula 4B-3] [Formula 4B-4]

In Formulas 4B-1 to 4B-4, Y ¹ , Y ² , X ² , R ¹⁹ to R ²³ , L ⁶ to L ⁸ , Ar ⁵ , Ar ⁶ , R ^c1 and R ^c4 are the same as described above.

Formula 4C may be, for example, represented by any one of the following Formulas 4C-1 to 4C-4, depending on the specific substitution position of the amine group.

[Formula 4C-1] [Formula 4C-2]

[Formula 4C-3] [Formula 4C-4]

In Formulas 4C-1 to 4C-4, Y ¹ , Y ² , X ² , R ¹⁹ to R ²³ , L ⁶ to L ⁸ , Ar ⁵ , Ar ⁶ , R ^c1 and R ^c2 are the same as described above.

Formula 4D may be, for example, represented by any one of the following Formulas 4D-1 to 4D-4 depending on the specific substitution position of the amine group.

[Formula 4D-1] [Formula 4D-2]

[Formula 4D-3] [Formula 4D-4]

In Formulas 4D-1 to 4D-4, Y ¹ , Y ² , X ² , R ¹⁹ to R ²³ , L ⁶ to L ⁸ , Ar ⁵ , Ar ⁶ , R ^c3 and R ^c4 are the same as described above.

Formula 4E may be, for example, represented by any one of the following Formulas 4E-1 to 4E-4 depending on the specific substitution position of the amine group.

[Formula 4E-1] [Formula 4E-2]

[Formula 4E-3] [Formula 4E-4]

In Formulas 4E-1 to 4E-4, Y ¹ , Y ² , X ² , R ¹⁹ to R ²³ , L ⁶ to L ⁸ , Ar ⁵ , Ar ⁶ , R ^c1 and R ^c4 are the same as described above.

Formula 4F may be, for example, represented by any one of the following Formulas 4F-1 to 4F-4 depending on the specific substitution position of the amine group.

[Formula 4F-1] [Formula 4F-2]

[Formula 4F-3] [Formula 4F-4]

In Formulas 4F-1 to 4F-4, Y ¹ , Y ² , X ² , R ¹⁹ to R ²³ , L ⁶ to L ⁸ , Ar ⁵ , Ar ⁶ , R ^c1 and R ^c2 are the same as described above.

As a specific example, the third compound may be represented by Formula 4A or Formula 4B.

As a more specific example, the first compound may be represented by Formula 4A-4 or Formula 4B-1.

The third compound may be, for example, one selected from the compounds listed in Group 3, but is not limited thereto.

[Group 3]

[3-1] [3-2] [3-3] [3-4]

[3-5] [3-6] [3-7] [3-8]

[3-9] [3-10] [3-11] [3-12]

[3-13] [3-14] [3-15] [3-16]

[3-17] [3-18] [3-19] [3-20]

[3-21] [3-22] [3-23] [3-24]

[3-25] [3-26] [3-27] [3-28]

[3-29] [3-30] [3-31] [3-32]

[3-33] [3-34] [3-35] [3-36]

[3-37] [3-38] [3-39] [3-40]

[3-41] [3-42] [3-43] [3-44]

[3-45] [3-46] [3-47] [3-48]

[3-49] [3-50] [3-51] [3-52]

[3-53] [3-54] [3-55] [3-56]

[3-57] [3-58] [3-59] [3-60]

[3-61] [3-62] [3-63] [3-64]

[3-65] [3-66] [3-67] [3-68]

[3-69] [3-70] [3-71] [3-72]

[3-73] [3-74] [3-75] [3-76]

[3-77] [3-78] [3-79] [3-80]

[3-81] [3-82] [3-83] [3-84]

[3-85] [3-86] [3-87] [3-88]

[3-89] [3-90] [3-91] [3-92] [3-93]

[3-94] [3-95] [3-96] [3-97]

[3-98] [3-99] [3-100] [3-101]

[3-102] [3-103] [3-104] [3-105]

[3-106] [3-107] [3-108] [3-109]

[3-110] [3-111] [3-112] [3-113]

[3-114] [3-115] [3-116] [3-117]

[3-118] [3-119] [3-120] [3-121]

[3-122] [3-123] [3-124] [3-125]

[3-126] [3-127] [3-128] [3-129]

[3-130] [3-131] [3-132] [3-133]

[3-134] [3-135] [3-136] [3-137]

[3-138] [3-139] [3-140] [3-141]

[3-142] [3-143] [3-144] [3-145]

[3-146] [3-147] [3-148] [3-149]

[3-150] [3-151] [3-152] [3-153]

[3-154] [3-155] [3-156] [3-157]

[3-158] [3-159] [3-160] [3-161]

[3-162] [3-163] [3-164] [3-165]

[3-166] [3-167] [3-168] [3-169]

[3-170] [3-171] [3-172] [3-173]

[3-174] [3-175] [3-176] [3-177]

[3-178] [3-179] [3-180] [3-181]

[3-182] [3-183] [3-184] [3-185]

[3-186] [3-187] [3-188] [3-189] [3-190]

According to the most specific embodiment of the present invention, the first compound is represented by Formula 1A, the second compound is represented by Formula 3-8, and the third compound is represented by Formula 4B-1. can be expressed as

The hole transport layer 141 is positioned between the anode 110 and the emission layer 130 , and may facilitate hole transport from the anode 110 to the emission layer 130 . For example, the hole transport layer 141 may include a material having a HOMO energy level between the work function of the conductor forming the anode 110 and the HOMO energy level of the material forming the light emitting layer 130 .

The hole transport layer 141 may include, for example, an amine derivative.

The hole transport layer 141 may include, for example, a compound represented by the following Chemical Formula 6, but is not limited thereto.

[Formula 6]

In Formula 6,

R ²⁴ to R ²⁷ are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heterocyclic group, or a combination thereof ,

R ²⁴ and R ²⁵ are each independently present or combine with each other to form a ring,

R ²⁶ and R ²⁷ are each independently present or combine with each other to form a ring,

Ar ⁷ To Ar ⁹ are each independently a substituted or unsubstituted C6 to C30 aryl group or a substituted or unsubstituted C2 to C30 heterocyclic group,

L ¹⁰ to L ¹³ are each independently a single bond, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C2 to C30 heterocyclic group, or a combination thereof.

For example, Ar ⁷ may be a substituted or unsubstituted C6 to C30 aryl group, for example, R ²⁶ may be a substituted or unsubstituted phenyl group or a substituted or unsubstituted biphenyl group.

For example, Ar ⁸ and Ar ⁹ are each independently a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted bisfluorene group, a substituted or unsubstituted a triphenylenyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, or a combination thereof .

The compound represented by Formula 6 may be, for example, one of the compounds listed in Group 4, but is not limited thereto.

[Group 4]

The organic layer 105 may further include an electron transport region (not shown) in addition to the light emitting layer 130 , the hole transport auxiliary layer 142 and the hole transport layer 141 .

The electron transport region may further increase electron injection and/or electron mobility between the cathode 110 and the emission layer 130 and block holes.

Specifically, the electron transport region 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, among the compounds listed in Group A below. At least one may be included in at least one of the electron transport layer and the electron transport auxiliary layer.

[Group A]

In another embodiment of the present invention, the organic layer 105 may be an organic light emitting device further including an electron injection layer, a hole injection layer, etc. in addition to the emission layer 130 .

After forming an anode or cathode on a substrate, the organic light emitting device 300 forms an organic layer by a dry film method or a solution process such as vacuum deposition, sputtering, plasma plating and ion plating, or the like. It can be manufactured by forming an anode or anode on it.

The above-described organic optoelectronic device may be applied to a display device. For example, the organic light emitting diode may be applied to an organic light emitting display device.

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

Hereinafter, unless otherwise specified, starting materials and reactants used in Examples and Synthesis Examples were purchased from Sigma-Aldrich, TCI, Tokyo chemical industry, or P&H tech, or synthesized through a known method.

A compound presented as a more specific example of the present invention was synthesized through the following steps.

(Preparation of first compound)

< Core Synthesis 1 >

Int-1 Int-2

Synthesis Example 1: Synthesis of Intermediate Int-1

[Scheme 1]

Int-1

4-Bromodibenzofuran (50 g, 202.36 mmol), 2-Chloroaniline (38.72 g, 303.53 mmol), Pd ₂ (dba) ₃ (9.26 g, 10.12 mmol), P(t-bu) ₃ (7.39 ml, 30.35 mmol) and NaO(t-Bu) (29.17g 303.53mmol) was placed in a round bottom flask, dissolved in toluene (650ml), and stirred under reflux at 130°C for 12 hours. When the reaction was completed, 38 g (64%) of the intermediate Int-1 was obtained by using column chromatography (Hexane: DCM (20%)) after removing the water layer.

Synthesis Example 2: Synthesis of Intermediate Int-2

[Scheme 2]

Int-1 Int-2

Intermediate Int-1 (50 g, 170.21 mmol), Pd ₂ (dba) ₃ (7.79 g, 8.51 mmol), CS ₂ CO ₃ (110.91 g, 340.43 mmol) and PCy3.H.BF ₄ ( 6.27 g, 17.02 mmol) was placed in a round-bottom flask, dissolved in DMAc (550 ml), and stirred under reflux at 160° C. for 12 hours. When the reaction is complete, an excess of distilled water is poured and stirred for 1 hour. After filtering the solids, dissolve them in hot MCB. After removing moisture with MgSO ₄ , the organic solvent is filtered using a silica gel pad, and the filtrate is stirred. When a solid was formed, it was filtered and vacuum dried to obtain 26.9 g (62%) of the intermediate Int-2.

Intermediates Int-3, Int-4, Int-5, Int-6, Int-7, and Int-8 were synthesized in the same manner as in Synthesis Examples 1 and 2 by changing the Bromo-dibenzofuran intermediate.

Int-3 Int-4 Int-5 Int-6

Int-7 Int-8

Synthesis Example 3: Synthesis of Intermediate Int-10

[Scheme 3]

Int-9 Int-10

2,4-Dichloro-6-phenyl-1,3,5-triazine (36 g, 159.25 mmol), intermediate Int-9 (4-biphenylboronic acid, 42.5 g, 151.67 mmol), K ₂ CO ₃ (41.92 g, 303.33 mmol) and Pd(PPh ₃ ) ₄ (5.26 g, 4.55 mmol) were placed in a round-bottom flask, dissolved in THF (500 ml) and distilled water (200 ml), and stirred under reflux at 60° C. for 12 hours. After completion of the reaction, the water layer was removed and the organic solvent was removed under reduced pressure to obtain a solid. The obtained solid is dissolved in hot MCB. After removing moisture with MgSO ₄ , the organic solvent is filtered using a silica gel pad, and the filtrate is stirred. When a solid was formed, it was filtered and dried under vacuum to obtain 28 g (52%) of the intermediate Int-10.

Intermediates Int-11 and Int-12 were synthesized in the same manner as in Synthesis Example 3, except that the triazine intermediate and Int-9 were changed.

Synthesis Example 4: Synthesis of compound 1-7

[Scheme 4]

Int-2 Int-10 1-7

Intermediate Int-2 (12g, 46.7mmol), Intermediate Int-10(2-chloro-4-(biphenyl-4-yl)-6-phenyl-1,3,5-triazine, 17.6g in a round-bottom flask under nitrogen condition , 51.35mmol), and NaH (3.17g, 79.35mmol) were placed in a round bottom flask, dissolved in DMF (230ml), and stirred under reflux at room temperature for 12 hours. When the reaction is complete, an excess of distilled water is poured and stirred for 1 hour. After filtering the solids, dissolve them in hot MCB. After removing moisture with MgSO ₄ , the organic solvent is filtered using a silica gel pad, and the filtrate is stirred. When a solid was formed, it was filtered and vacuum dried to obtain 23.7 g (90%) of compound 1-7.

The following compounds were synthesized in the same manner as in Synthesis Example 4, except that the intermediate was changed as shown in Table 1 below.

division Intermediate 1 Intermediate 2 yield
(transference number) final product Synthesis example
5 Int-3 Int-10 13.4g
(74%) 1-8 Synthesis example
6 Int-4 Int-10 9.6g
62% 1-10 Synthesis example
7 Int-5 Int-10 17.1g
89% 1-11 Synthesis example
8 Int-6 Int-10 11.3g
71% 1-12 Synthesis example
9 Int-7 Int-10 6.1g
68% 1-91 Synthesis example
10 Int-8 Int-10 4.2g
57% 1-94 Synthesis example
11 Int-2 Int-11 13.2g
94% 1-13 Synthesis example
12 Int-4 Int-11 10.8g
78% 1-16 Synthesis example
13 Int-7 Int-11 7.8g
54% 1-97 Synthesis example
14 Int-8 Int-11 5.5g
45% 1-100 Synthesis example
15 Int-2 Int-12 12.7g
87% 1-79 Synthesis example
16 Int-4 Int-12 10.7g
83% 1-82 Synthesis example
17 Int-7 Int-12 8.8g
76% 1-159 Synthesis Example 18 Int-8 Int-12 5.3g
71% 1-162

Int-11 Int-12

(Preparation of second compound)

Synthesis Example 19: Synthesis of compound 2-142

Compound 2-142 was synthesized with reference to a method known from KR 10-1773363 B1.

Synthesis Example 20: Synthesis of compound 2-99

Compound 2-99 was synthesized with reference to a method known from KR 10-1773363 B1.

(Preparation of the third compound)

Synthesis Example 21: Synthesis of compound 3-20

Compound 3-20 was synthesized with reference to a method known to KR 10-2018-0037889 A.

Synthesis Example 22: Synthesis of compound 3-28

Compound 3-28 was synthesized with reference to a method known to KR 10-2018-0037889 A.

Comparative Synthesis Example 1: Synthesis of compound P-1

Compound P-1 was synthesized with reference to a method known from KR 10-1476231 B1.

Comparative Synthesis Example 2: Synthesis of compound P-2

[Scheme 5]

P-2

Bis(4-biphenylyl)amine (10g, 31.14mmol), 2-Chloro-9, 9-diphenyl-9H-fluorene (10.4g, 29.66mmol), NaOtBu (4.28g, 44.48mmol), Pd ₂ (dba) ₃ (1.63 g, 1.78 mmol) and SPhos (2.19 g, 5.34 mmol) were placed in a round-bottom flask, dissolved in toluene (150 ml), and stirred under reflux at 90° C. for 4 hours. When the reaction is complete, an excess of distilled water is poured in, and the organic layer is separated using a separatory funnel. The product thus obtained was dried with MgSO ₄ , and then 10.5 g (56%) of compound P-2 was obtained by column chromatography (Hexane: DCM (20%)).

Comparative Synthesis Example 3: Synthesis of Intermediate Int-13

[Scheme 6]

Int-13

9H-Carbazole-3-boronic acid pinacol ester (20g, 68.22mmol), ₂ - _{Bromodibenzothiophene} (17.87g, 68.22mmol), K2CO3 (18.86g, 136.44mmol) and Pd(PPh) in a round-bottom flask under nitrogen condition. ₃ ) ₄ (3.94g, 3.41mmol) was placed in a round-bottom flask, dissolved in THF (230ml) and distilled water (80ml), and stirred under reflux at 60°C for 12 hours. After completion of the reaction, the water layer was removed and the organic solvent was removed under reduced pressure to obtain a solid. The obtained solid is dissolved in hot MCB. After removing moisture with MgSO ₄ , the organic solvent is filtered using a silica gel pad, and the filtrate is stirred. When a solid was formed, it was filtered and vacuum dried to obtain 14.77 g (62%) of the intermediate Int-13.

Comparative Synthesis Example 4: Synthesis of compound H-1

[Scheme 7]

Int-13H-1

Intermediate Int-13 (14.77 g, 42.31 mmol), 2- (3- Bromophenyl) - 4, 6-diphenyl- 1, 3, 5- triazine (16.38 g, 42.31 mmol), NaOtBu (5.03) in a round-bottom flask under nitrogen condition g, 50.77 mmol), Pd ₂ (dba) ₃ (2.32 g, 2.54 mmol), and P(t-Bu) ₃ (1.03ml, 4.23mmol) was placed in a round bottom flask, dissolved in xylene (150ml), and stirred under reflux at 120°C for 12 hours. When the reaction is complete, an excess of distilled water is poured and stirred for 1 hour. After filtering the solids, dissolve them in hot MCB. After removing moisture with MgSO ₄ , the organic solvent is filtered using a silica gel pad, and the filtrate is stirred. When a solid was formed, it was filtered and vacuum dried to obtain 20 g (72%) of compound H-1.

(Production of organic light emitting device)

Example 1

A glass substrate coated with a thin film of ITO (Indium tin oxide) was washed with distilled water and ultrasonic waves. After washing with distilled water, ultrasonic cleaning is performed with a solvent such as isopropyl alcohol, acetone, methanol, etc., dried, and transferred to a plasma cleaner. After cleaning the substrate using oxygen plasma for 10 minutes, the substrate is transferred to a vacuum evaporator. Using the prepared ITO transparent electrode as an anode, vacuum deposition of Compound A doped with 1% NDP-9 (commercially available from Novaled) on an ITO substrate to form a hole transport layer with a thickness of 1400 Å was synthesized on the hole transport layer Compound 3-20 obtained in Example 21 was deposited to a thickness of 350 Å to form a hole transport auxiliary layer. Compound 1-7 obtained in Synthesis Example 4 and compound 2-142 obtained in Synthesis Example 19 were simultaneously used as hosts on the hole transport auxiliary layer, and PhGD was doped at 10wt% as a dopant to form a 400Å-thick light emitting layer by vacuum deposition. . Here, compound 1-7 and compound 2-142 were used in a weight ratio of 4:6. Subsequently, compound C was deposited on the light emitting layer to a thickness of 50 Å to form an electron transport auxiliary layer, and compound D and Liq were simultaneously vacuum deposited at a weight ratio of 1:1 to form an electron transport layer having a thickness of 300 Å. An organic light emitting diode was manufactured by sequentially vacuum-depositing LiQ 15 Å and Al 1200 Å on the electron transport layer to form a cathode.

ITO / Compound A (1% NDP-9 doping, 1400Å) / Compound 3-20 (350Å) / EML [Compound 1-7: Compound 2-142: PhGD = 4:6:10wt%] (400Å) / Compound C (50Å) / Compound D: LiQ (300Å) / LiQ (15Å) / Al (1200Å) was prepared in the structure.

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

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

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

[PhGD]

Examples 2 to 4, and Comparative Examples 1 to 3

Devices of Examples 2 to 4 and Comparative Examples 1 to 3 were manufactured in the same manner as in Example 1, except that the host or hole transport auxiliary layer was changed as shown in Tables 2 and 3 below.

evaluation

The driving voltage and lifespan characteristics of the organic light emitting diodes according to Examples 1 to 4 and Comparative Examples 1 to 3 were evaluated. Specific measurement methods are as follows, and the results are shown in Tables 2 and 3.

(1) Measurement of change in current density according to voltage change

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

(2) Measurement of luminance change according to voltage change

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

(3) Lifetime measurement

For the manufactured organic light emitting device, the initial luminance (cd/m ² ) was emitted at 24,000 cd/m ² for the devices of Examples 1 to 4 and Comparative Examples 1 to 3 using the Polaronics lifetime measurement system, and By measuring the decrease in luminance over time, the time when the luminance decreased to 98% compared to the initial luminance was measured as the T98 lifetime.

(4) Measurement of driving voltage

A current-voltmeter (Keithley 2400) was used to measure the driving voltage of each device at 15mA/cm ² , and the results were obtained.

(5) T98 life ratio (%) calculation

Table 3 shows the relative comparative values of T98(h) between Example 4 and Comparative Example 3.

T98 life ratio (%) = {T98 (h) of Example 4 / T98 (h) of Comparative Example 3} X 100

(6) Calculation of driving voltage ratio (%)

Table 2 shows the relative comparison values of the driving voltages of Example 1, Examples 2 and 3, and Comparative Examples 1 and 2.

Drive voltage ratio (%) = {Drive voltage (V) of Example 1 / Drive voltage (V) of (Comparative Examples 1 and 2 or Examples 2 and 3)} X 100

light emitting layer hole transport auxiliary layer Driving voltage ratio (%) first compound second compound third compound Example 1 1-7 2-142 3-20 100% Example 2 1-13 2-142 3-20 99% Example 3 1-79 2-142 3-20 99% Comparative Example 1 1-7 2-142 P-1 113% Comparative Example 2 1-7 2-142 P-2 111%

light emitting layer hole transport auxiliary layer T98 Life Ratio (%) first compound second compound third compound Example 4 1-7 2-99 3-20 100% Comparative Example 3 H-1 2-99 3-20 40%

Referring to Table 2, it can be seen that the organic light emitting devices according to Examples 1 to 3 have lower driving voltages compared to the organic light emitting devices according to Comparative Examples 1 and 2. These results show that, in the hole transport auxiliary layer in the organic light emitting device according to Examples 1 to 3, the compound represented by the combination of Formulas 4 and 5, which has superior hole transport ability compared to the organic light emitting devices according to Comparative Examples 1 and 2, is used. This is because the overall charge balance in the device is achieved.

Also, referring to Table 3, it can be seen that the organic light emitting device according to Example 4 has improved lifespan characteristics compared to the organic light emitting device according to Comparative Example 3. This result is because the compound represented by the combination of Chemical Formulas 1 and 2 capable of implementing superior hole injection and transport characteristics compared to the organic light emitting diode according to Comparative Example 3 was used in the light emitting layer in the organic light emitting device according to Example 4. The compound represented by the combination of Chemical Formulas 1 and 2 expands the HOMO electron cloud as benzofuran or benzothiophene is fused to the carbazole moiety, and exhibits smooth hole injection and transport properties. The stability due to the hole and electron balance can improve the lifetime characteristics.

That is, the combination of the compound represented by the combination of Formulas 1 to 2, the compound represented by Formula 3, and the compound represented by the combination of Formulas 4 and 5 exhibits significantly superior performance compared to other combinations, so it is the most ideal combination. Able to know.

Although preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements by those skilled in the art using the basic concept of the present invention as defined in the following claims are also presented. It belongs to the scope of the invention.

300: organic light emitting device
110: positive electrode
120: cathode
130: light emitting layer
141: hole transport layer
142: hole transport auxiliary layer
105: organic layer

Claims (14)

positive and negative poles facing each other,
a light emitting layer positioned between the anode and the cathode;
a hole transport layer positioned between the anode and the light emitting layer, and
A hole transport auxiliary layer positioned between the light emitting layer and the hole transport layer
including,
The light emitting layer includes a first compound represented by a combination of Formula 1 and Formula 2 below and a second compound represented by Formula 3 below,
The hole transport auxiliary layer is an organic optoelectronic device comprising a third compound represented by a combination of Chemical Formula 4 and Chemical Formula 5:
[Formula 1] [Formula 2]

In Formula 1 and Formula 2,
L ¹ to L ³ are each independently a single bond, a substituted or unsubstituted C6 to C20 arylene group, or a substituted or unsubstituted C2 to C20 heterocyclic group,
Ar ¹ and Ar ² are each independently a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heterocyclic group,
X ¹ is O or S,
a ₁ * to a ₄ * are each independently a linking carbon (C) or CR ^a ,
Adjacent two of a ₁ * to a ₄ * of Formula 1 are each connected to Formula 2,
* is the connection point,
R ^a and R ¹ to R ⁸ are each independently hydrogen, deuterium, a cyano group, a halogen 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;
[Formula 3]

In Formula 3,
Ar ³ and Ar ⁴ are each independently a substituted or unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted C2 to C30 heterocyclic group,
L ⁴ and L ⁵ are each independently a single bond, or a substituted or unsubstituted C6 to C20 arylene group,
R ^b and R ⁹ to R ¹⁸ are each independently hydrogen, deuterium, a cyano group, a halogen group, a substituted or unsubstituted amine group, a substituted or unsubstituted C1 to C30 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group , or a substituted or unsubstituted C2 to C30 heterocyclic group,
m is an integer from 0 to 2;
[Formula 4] [Formula 5]

In Chemical Formulas 4 and 5,
Y ¹ and Y ² are each independently a substituted or unsubstituted C1 to C30 alkyl group or a substituted or unsubstituted C6 to C30 aryl group,
X ² is O or S,
b ₁ * to b ₄ * are each independently a linking carbon (C) or CR ^c ,
Two adjacent ones of b ₁ * to b ₄ * of Formula 4 are each connected to Formula 5,
* is the connection point,
R ^c and R ¹⁹ to R ²³ are each independently hydrogen, deuterium, a cyano group, a halogen 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,
L ⁶ To L ⁸ are each independently a single bond, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heterocyclic group, or a combination thereof,
Ar ⁵ and Ar ⁶ are each independently a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heterocyclic group. The method of claim 1,
The first compound is represented by any one of the following Chemical Formulas 1A to 1F, an organic optoelectronic device:
[Formula 1A] [Formula 1B]

[Formula 1C] [Formula 1D]

[Formula 1E] [Formula 1F]

In Formula 1A to Formula 1F,
L ¹ to L ³ , Ar ¹ , Ar ² , X ¹ and R ¹ to R ⁸ are as defined in claim 1,
R ^a1 to R ^a4 are each independently the same as the definition of R ^a defined in claim 1 . According to claim 1,
L ² and L ³ are each independently a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted dibenzofuranylene group, a substituted or unsubstituted dibenzothiophenylene group, or a substituted or unsubstituted carba An organic optoelectronic device that is a zolylene group. According to claim 1,
wherein Ar ¹ and Ar ² are each independently a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, or a substituted or unsubstituted An organic optoelectronic device that is a cyclic carbazolyl group. According to claim 1,
The L ² -Ar ¹ and L ³ -Ar ² are each independently one selected from the substituents listed in the following group I organic optoelectronic device:
[Group I]

In the above group I, * is a connection point. The method of claim 1,
The first compound is a composition for an organic optoelectronic device which is one selected from the compounds listed in Group 1:
[Group 1]
[1-1] [1-2] [1-3] [1-4]

[1-5] [1-6] [1-7] [1-8]

[1-9] [1-10] [1-11] [1-12]

[1-13] [1-14] [1-15] [1-16]

[1-17] [1-18] [1-19] [1-20]

[1-21] [1-22] [1-23] [1-24]

[1-25] [1-26] [1-27] [1-28]

[1-29] [1-30] [1-31] [1-32]

[1-33] [1-34] [1-35] [1-36]

[1-37] [1-38] [1-39] [1-40]

[1-41] [1-42] [1-43] [1-44]

[1-45] [1-46] [1-47] [1-48]

[1-49] [1-50] [1-51] [1-52]

[1-53] [1-54] [1-55] [1-56]

[1-57] [1-58] [1-59] [1-60]

[1-61] [1-62] [1-63] [1-64]

[1-65] [1-66] [1-67] [1-68]

[1-69] [1-70] [1-71] [1-72]

[1-73] [1-74] [1-75] [1-76]

[1-77] [1-78] [1-79] [1-80]

[1-81] [1-82] [1-83] [1-84]

[1-85] [1-86] [1-87] [1-88]

[1-89] [1-90] [1-91] [1-92]

[1-93] [1-94] [1-95] [1-96]

[1-97] [1-98] [1-99] [1-100]

[1-101] [1-102] [1-103] [1-104]

[1-105] [1-106] [1-107] [1-108]

[1-109] [1-110] [1-111] [1-112]

[1-113] [1-114] [1-115] [1-116]

[1-117] [1-118] [1-119] [1-120]

[1-121] [1-122] [1-123] [1-124]

[1-125] [1-126] [1-127] [1-128]

[1-129] [1-130] [1-131] [1-132]

[1-133] [1-134] [1-135] [1-136]

[1-137] [1-138] [1-139] [1-140]

[1-141] [1-142] [1-143] [1-144]

[1-145] [1-146] [1-147] [1-148]

[1-149] [1-150] [1-151] [1-152]

[1-153] [1-154] [1-155] [1-156]

[1-157] [1-158] [1-159] [1-160]

[1-161] [1-162] [1-163] [1-164]

. The method of claim 1,
The second compound is an organic optoelectronic device represented by the following Chemical Formula 3-8:
[Formula 3-8]

In Formula 3-8,
R ⁹ to R ¹⁸ are each independently hydrogen, or a substituted or unsubstituted C6 to C12 aryl group,
*-L ⁴ -Ar ³ and *-L ⁵ -Ar ⁴ are each independently one of the substituents listed in Group II,
[Group II]

In the above group II, * is a connection point. The method of claim 1,
The third compound is represented by any one of the following Chemical Formulas 4A to 4F, an organic optoelectronic device:
[Formula 4A] [Formula 4B]

[Formula 4C] [Formula 4D]

[Formula 4E] [Formula 4F]

In Formulas 4A to 4F,
Y ¹ , Y ² , X ² , R ¹⁹ to R ²³ , L ⁶ to L ⁸ , Ar ⁵ and Ar ⁶ are the same as in claim 1 ,
R ^c1 to R ^c4 are each independently the same as the definition of R ^c defined in claim 1 . According to claim 1,
The L ⁷ and L ⁸ are each independently a single bond, a substituted or unsubstituted phenylene group, or a substituted or unsubstituted naphthylene group, an organic optoelectronic device. The method of claim 1,
wherein Ar ⁵ and Ar ⁶ are each 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, Organic which is a substituted or unsubstituted phenanthrenyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, or a substituted or unsubstituted carbazolyl group optoelectronic devices. The method of claim 1,
The L ⁷ -Ar ⁵ and L ⁸ -Ar ⁶ are each independently any one selected from the substituents listed in the following group Ⅲ organic optoelectronic device:
[Group III]

In the above group III, * is a connection point. The method of claim 1,
The third compound is any one selected from the compounds listed in Group 3, an organic optoelectronic device:
[Group 3]
[3-1] [3-2] [3-3] [3-4]

[3-5] [3-6] [3-7] [3-8]

[3-9] [3-10] [3-11] [3-12]

[3-13] [3-14] [3-15] [3-16]

[3-17] [3-18] [3-19] [3-20]

[3-21] [3-22] [3-23] [3-24]

[3-25] [3-26] [3-27] [3-28]

[3-29] [3-30] [3-31] [3-32]

[3-33] [3-34] [3-35] [3-36]

[3-37] [3-38] [3-39] [3-40]

[3-41] [3-42] [3-43] [3-44]

[3-45] [3-46] [3-47] [3-48]

[3-49] [3-50] [3-51] [3-52]

[3-53] [3-54] [3-55] [3-56]

[3-57] [3-58] [3-59] [3-60]

[3-61] [3-62] [3-63] [3-64]

[3-65] [3-66] [3-67] [3-68]

[3-69] [3-70] [3-71] [3-72]

[3-73] [3-74] [3-75] [3-76]

[3-77] [3-78] [3-79] [3-80]

[3-81] [3-82] [3-83] [3-84]

[3-85] [3-86] [3-87] [3-88]

[3-89] [3-90] [3-91] [3-92] [3-93]

[3-94] [3-95] [3-96] [3-97]

[3-98] [3-99] [3-100] [3-101]

[3-102] [3-103] [3-104] [3-105]

[3-106] [3-107] [3-108] [3-109]

[3-110] [3-111] [3-112] [3-113]

[3-114] [3-115] [3-116] [3-117]

[3-118] [3-119] [3-120] [3-121]

[3-122] [3-123] [3-124] [3-125]

[3-126] [3-127] [3-128] [3-129]

[3-130] [3-131] [3-132] [3-133]

[3-134] [3-135] [3-136] [3-137]

[3-138] [3-139] [3-140] [3-141]

[3-142] [3-143] [3-144] [3-145]

[3-146] [3-147] [3-148] [3-149]

[3-150] [3-151] [3-152] [3-153]

[3-154] [3-155] [3-156] [3-157]

[3-158] [3-159] [3-160] [3-161]

[3-162] [3-163] [3-164] [3-165]

[3-166] [3-167] [3-168] [3-169]

[3-170] [3-171] [3-172] [3-173]

[3-174] [3-175] [3-176] [3-177]

[3-178] [3-179] [3-180] [3-181]

[3-182] [3-183] [3-184] [3-185]

[3-186] [3-187] [3-188] [3-189] [3-190]

. The method of claim 1,
The first compound is represented by the following formula 1A,
The second compound is represented by the following Chemical Formula 3-8,
The third compound is an organic optoelectronic device that is represented by the following Chemical Formula 4B-1:
[Formula 1A]

In Formula 1A,
X ¹ is O or S,
L ¹ is a single bond,
L ² and L ³ are each independently a single bond, a substituted or unsubstituted phenylene group, or a substituted or unsubstituted carbazolylene group,
Ar ¹ and Ar ² are each independently a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, or a substituted or unsubstituted carbazolyl group,
R ^a3 , R ^a4 and R ¹ to R ⁸ are each independently hydrogen or a substituted or unsubstituted phenyl group;
[Formula 3-8]

In Formula 3-8,
Ar ³ and Ar ⁴ are each independently a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted di a benzothiophenyl group,
L ⁴ and L ⁵ are each independently a single bond, or a substituted or unsubstituted C6 to C20 arylene group,
R ⁹ to R ¹⁸ are each independently hydrogen, deuterium, a cyano group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted dibenzothiophenyl group;
[Formula 4B-1]

In Formula 4B-1,
X ² is O or S,
L ⁶ is a single bond or a substituted or unsubstituted phenylene group,
L ⁷ and L ⁸ are each independently a single bond, or a substituted or unsubstituted phenylene group,
Ar ⁵ and Ar ⁶ are each independently a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, or a substituted or unsubstituted fluorenyl group,
Y ¹ and Y ² are each independently a substituted or unsubstituted C1 to C5 alkyl group or a substituted or unsubstituted C6 to C12 aryl group,
R ^c1 , R ^c4 and R ¹⁹ to R ²³ are each hydrogen. A display device comprising the organic optoelectronic device according to any one of claims 1 to 13.

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