TWI703203B - Organic optoelectric device and display device - Google Patents

Abstract

Disclosed are an organic optoelectric device including an anode and a cathode facing each other, a light emitting layer disposed between the anode and the cathode, hole transport layer disposed between the anode and the light emitting layer, and a hole transport auxiliary layer disposed between the light emitting layer and the hole transport layer, wherein the light emitting layer includes a first compound represented by Chemical Formula 1 and a second compound represented by a combination of Chemical Formula 2 and Chemical Formula 3, and the hole transport auxiliary layer includes a third compound represented by Chemical Formula 4 and a display device including the same. Chemical Formulae 1 to 4 are the same as provided in the specification.

Description

Organic photoelectric device and display device

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

Organic photoelectric devices (organic photodiodes) are devices that convert electrical energy into light energy and vice versa.

Organic photoelectric devices can be classified as follows according to their driving principles. One is a photoelectric device in which excitons are generated by light energy, which are separated into electrons and holes and transferred to different electrodes to generate electrical energy, and the other is a light emitting device, in which voltage or current is supplied to the electrodes to be Electricity generates light energy.

Examples of organic photoelectric devices may be organic photoelectric devices, organic light-emitting diodes, organic solar cells, and organic photo conductor drums.

Among them, organic light emitting diodes (OLEDs) have recently attracted attention due to the increasing demand for flat panel displays. The organic light emitting diode converts electrical energy into light by applying current to the organic light emitting material, and the efficiency of the organic light emitting diode can be affected by the organic material disposed between the electrodes.

An embodiment provides an organic photoelectric device capable of improving power efficiency by reducing the driving voltage.

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

According to an embodiment, an organic optoelectronic device includes: an anode and a cathode facing each other; a light-emitting layer disposed between the anode and the cathode; a hole transport layer disposed between the anode and the light-emitting layer And a hole transport auxiliary layer disposed between the light emitting layer and the hole transport layer, wherein the light emitting layer includes a first compound represented by chemical formula 1 and a first compound represented by a combination of chemical formula 2 and chemical formula 3 Two compounds, and the hole transport auxiliary layer includes a third compound represented by Chemical Formula 4.

In chemical formula 1, X ¹ is O or S, Z ¹ to Z ^{3 are} independently N or CR ^a , at least two of Z ¹ to Z ³ are N, and Ar ¹ and Ar ^{2 are} independently hydrogen, substituted Or unsubstituted C6 to C30 aryl, substituted or unsubstituted C2 to C30 heterocyclic group or a combination thereof, L ¹ to L ^{3 are} independently single bonds, substituted or unsubstituted C6 to C30 extensions an aryl group, a divalent C2 to C30 via a substituted or unsubstituted heterocyclic group or a combination thereof, R ¹ to R ⁵ and R ^a is independently hydrogen, deuterium, substituted or unsubstituted C1 to C20 alkyl, Substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C3 to C30 heterocyclic group, substituted or unsubstituted silyl group, substituted or unsubstituted amine group, halogen, cyano Group or a combination thereof, R ¹ to R ³ exist independently or two adjacent ones of R ¹ to R ³ are combined to form a ring, and R ⁴ and R ⁵ exist independently or are fused with each other to form a ring,

Wherein, in Chemical Formula 2 or Chemical Formula 3, Y ¹ and Y ^{2 are} independently a single bond or a substituted or unsubstituted C6 to C30 arylene group, and A ¹ and A ^{2 are} independently substituted or unsubstituted C6 to C30 aryl groups, two adjacent * of formula 2 are bonded to two * of formula 3, and the remaining two * of formula 2 are CR ^b and CR ^c , R ²⁰ to R ²³ , R ^b and R ^{c is} independently hydrogen, deuterium, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C3 to C30 heterocyclic group, or a combination thereof , R ²⁰ and R ²¹ exist independently or fused with each other to form a ring, and R ²² and R ²³ exist independently or fused with each other to form a ring,

Wherein, in the chemical formula 4, L ⁴ to L ^{9 are} independently a single bond, a substituted or unsubstituted C6 to C30 arylene group, a divalent substituted or unsubstituted C2 to C30 heterocyclic group, or a combination thereof , R ⁵⁰ to R ^{55 are} independently hydrogen, deuterium, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C3 to C30 hetero Cyclic group, substituted or unsubstituted silyl group, substituted or unsubstituted amine group, halogen, cyano group or a combination thereof, R ⁵⁰ and R ^{51 are} independently present or fused with each other to form a ring, R ⁵² and R ⁵³ independently exists or is fused with each other to form a ring, and R ⁵⁴ and R ⁵⁵ independently exist or are fused with each other to form a ring.

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

An organic photoelectric device with high efficiency and long life can be achieved.

105: organic layer

110: anode

120: cathode

130: luminescent layer

141: hole transport layer

142: hole transmission auxiliary layer

300: organic light emitting diode

FIG. 1 is a schematic cross-sectional view of an organic photoelectric device according to an embodiment.

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

In this specification, when no other definition is provided, "substituted" means that at least one hydrogen of a substituent or compound is replaced by deuterium, halogen, hydroxyl, amine, substituted or unsubstituted C1 to C30 Amino, nitro, 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, C6 to C30 aryl, C2 to C30 heteroaryl, C1 to C20 alkoxy, C1 to C10 trifluoroalkyl, cyano or a combination thereof.

In an example of the present invention, "substituted" means that at least one hydrogen of a substituent or compound is deuterated, C1 to C30 alkyl, C1 to C10 alkylsilyl, C6 to C30 arylsilyl, C3 to C30 Cycloalkyl, C3 to C30 heterocycloalkyl, C6 to C30 aryl or C2 to C30 heteroaryl replacement. In addition, in specific examples of the present invention, "substituted" means that at least one hydrogen of a substituent or compound is replaced by deuterium, a C1 to C20 alkyl group, a C6 to C30 aryl group, or a C2 to C30 heteroaryl group. In addition, in the specific examples of the present invention, "substituted" means that at least one hydrogen of a substituent or compound is deuterated, C1 to C5 alkyl, C6 to C18 aryl, pyridyl, quinolyl, isoquinolyl , Dibenzofuranyl, dibenzothienyl or carbazolyl substitution. In addition, in the specific examples of the present invention, "substituted" means that at least one hydrogen of a substituent or compound is deuterated, C1 to C5 alkyl, C6 to C18 aryl, dibenzofuranyl or dibenzothienyl Replacement. In addition, in the specific examples of the present invention, "substituted" means that at least one hydrogen of a substituent or compound is deuterated, methyl, ethyl, propyl, butyl, phenyl, biphenyl, terphenyl, Naphthyl, triphenyl, dibenzofuranyl or dibenzothienyl substitution.

In this specification, when no additional definition is provided, "hetero" means that one functional group includes one to three heteroatoms selected from N, O, S, P, and Si, and the rest are carbon.

In this specification, "aryl" refers to a group containing at least one hydrocarbon aromatic moiety, and all elements of the hydrocarbon aromatic moiety have p-orbitals forming conjugates, such as phenyl, naphthyl, etc., two or More hydrocarbon aromatic moieties can be connected by σ bonds, and can be, for example, biphenyl, terphenyl, tetraphenyl, etc., and two or more hydrocarbon aromatic moieties are directly or indirectly fused (fuse ) To provide a non-aromatic fused ring, such as a fluorenyl group.

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

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

For example, "heteroaryl group" may refer to an aryl group including at least one heteroatom selected from N, O, S, P, and Si instead of carbon (C). Two or more heteroaryl groups are directly connected by a σ bond, or when the C2 to C60 heteroaryl group includes two or more rings, the two or more rings may be fused. When the heteroaryl group is a fused ring, each ring may contain 1 to 3 heteroatoms.

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

基(chrysenyl group)、經取代或未經取代的聯三伸苯基、經取代或未經取代的苝基(perylenyl group)、經取代或未經取代的茀基、經取代或未經取代的茚基(indenyl group)、經取代或未經取代的呋喃基、經取代或未經取 代的噻吩基、經取代或未經取代的吡咯基、經取代或未經取代的吡唑基、經取代或未經取代的咪唑基、經取代或未經取代的三唑基、經取代或未經取代的噁唑基、經取代或未經取代的噻唑基、經取代或未經取代的噁二唑基、經取代或未經取代的噻二唑基、經取代或未經取代的吡啶基、經取代或未經取代的嘧啶基、經取代或未經取代的吡嗪基、經取代或未經取代的三嗪基、經取代或未經取代的苯並呋喃基、經取代或未經取代的苯並噻吩基、經取代或未經取代的苯並咪唑基、經取代或未經取代的吲哚基、經取代或未經取代的喹啉基、經取代或未經取代的異喹啉基、經取代或未經取代的喹唑啉基、經取代或未經取代的喹噁啉基、經取代或未經取代的萘啶基、經取代或未經取代的苯並噁嗪基、經取代或未經取代的苯並噻嗪基、經取代或未經取代的吖啶基(acridinyl group)、經取代或未經取代的啡嗪基、經取代或未經取代的啡噻嗪基、經取代或未經取代的啡噁嗪基、經取代或未經取代的二苯並呋喃基或者經取代或未經取代的二苯並噻吩基或其組合，但並非僅限於此。 More specifically, the substituted or unsubstituted C6 to C30 aryl group and/or the substituted or unsubstituted C2 to C30 heterocyclic group may be substituted or unsubstituted phenyl, substituted or unsubstituted Substituted naphthyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted naphthacenyl group, substituted or unsubstituted pyrenyl (pyrenyl group), substituted or unsubstituted biphenyl, substituted or unsubstituted p-terphenyl, substituted or unsubstituted m-terphenyl, substituted or unsubstituted o-terphenyl Radical, substituted or unsubstituted

Group (chrysenyl group), substituted or unsubstituted phenylene terpenide, substituted or unsubstituted perylenyl group, substituted or unsubstituted chrysenyl group, substituted or unsubstituted Indenyl group, substituted or unsubstituted furanyl, substituted or unsubstituted thienyl, substituted or unsubstituted pyrrolyl, substituted or unsubstituted pyrazolyl, substituted Or unsubstituted imidazolyl, substituted or unsubstituted triazolyl, substituted or unsubstituted oxazolyl, substituted or unsubstituted thiazolyl, substituted or unsubstituted oxadiazole Group, substituted or unsubstituted thiadiazolyl, substituted or unsubstituted pyridinyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted pyrazinyl, substituted or unsubstituted Substituted triazinyl, substituted or unsubstituted benzofuranyl, substituted or unsubstituted benzothienyl, substituted or unsubstituted benzimidazolyl, substituted or unsubstituted indole Dole, substituted or unsubstituted quinolinyl, substituted or unsubstituted isoquinolinyl, substituted or unsubstituted quinazolinyl, substituted or unsubstituted quinolinyl, The substituted or unsubstituted naphthyridinyl group, the substituted or unsubstituted benzoxazinyl group, the substituted or unsubstituted benzothiazinyl group, the substituted or unsubstituted acridinyl group (acridinyl group ), substituted or unsubstituted phenanthrazinyl, substituted or unsubstituted phenanthiazinyl, substituted or unsubstituted phenanthrazinyl, substituted or unsubstituted dibenzofuranyl or The substituted or unsubstituted dibenzothienyl group or a combination thereof is not limited to this.

In this specification, hole characteristics refer to the ability to donate electrons to form holes when an electric field is applied, and due to the conduction characteristics based on the energy level of the highest occupied molecular orbital (HOMO), The holes formed in the anode can be easily injected into the light-emitting layer and the holes formed in the light-emitting layer can be easily transported into the anode and in the light-emitting layer.

In addition, electronic characteristics refer to the ability to accept electrons when an electric field is applied, and And due to the conduction characteristics based on the lowest unoccupied molecular orbital (LUMO) energy level, the electrons formed in the cathode can be easily injected into the light-emitting layer and the electrons formed in the light-emitting layer can be easily transported to the cathode. And transmit in the light-emitting layer.

Hereinafter, an organic photoelectric device according to an embodiment is explained.

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

In this article, the organic light emitting diode is described as an example of the organic photoelectric device, but the present invention is not limited to this, but can be applied to other organic photoelectric devices in the same manner.

In the drawings, the thickness of layers, films, plates, regions, etc. are exaggerated for clarity. Throughout the specification, the same reference numbers designate the same elements. It should be understood that when an element (for example, a layer, film, region, or substrate) is referred to as being "on" another element, the element can be directly on the other element, or intervening elements may also be present. In contrast, when one element is said to be "directly on" another element, there is no intermediate element.

FIG. 1 is a schematic cross-sectional view of an organic photoelectric device according to an embodiment.

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 disposed between the anode 110 and the cathode 120, wherein the organic layer 105 includes a light emitting layer 130 and a hole Transmission auxiliary layer 142 and hole transmission layer 141.

The anode 110 may be made of a conductor having a large work function to facilitate hole injection, and may be, for example, a metal, a metal oxide, and/or a conductive polymer. The anode 110 can be, for example, metal nickel, platinum, vanadium, chromium, copper, zinc, gold, etc. or alloys thereof; metal oxides, such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide ( indium zinc oxide, IZO), etc.; 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) (poly(3,4-(ethylene-1,2-dioxy)thiophene), PEDT), polypyrrole and polyaniline, but not limited to this.

The cathode 120 may be made of a conductor having a small work function to facilitate electron injection, and may be, for example, a metal, a metal oxide, and/or a conductive polymer. The cathode 120 can be, for example, a metal or an alloy thereof, such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gamma, aluminum, silver, tin, lead, cesium, barium, etc.; -layer) Structural materials, such as LiF/Al, LiO ₂ /Al, LiF/Ca, LiF/Al, and BaF ₂ /Ca, but not limited to this.

The light-emitting layer 130 is disposed between the anode 110 and the cathode 120, and includes a variety of hosts and at least one dopant.

The light emitting layer 130 may include a first compound having relatively strong electronic characteristics and a second compound having relatively strong hole characteristics as a host.

The first compound having relatively strong electronic characteristics can be represented by Chemical Formula 1.

[Chemical formula 1]

In Chemical Formula 1, X ¹ is O or S, Z ¹ to Z ^{3 are} independently N or CR ^a , at least two of Z ¹ to Z ³ are N, and Ar ¹ and Ar ^{2 are} independently hydrogen, deuterium, A substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heterocyclic group or a combination thereof, L ¹ to L ^{3 are} independently a single bond, a substituted or unsubstituted C6 to C30 aryl group, divalent substituted or unsubstituted C2 to C30 heterocyclic group or a combination thereof, R ¹ to R ⁵ and R ^{a are} independently hydrogen, deuterium, substituted or unsubstituted C1 to C20 alkane Group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C3 to C30 heterocyclic group, substituted or unsubstituted silyl group, substituted or unsubstituted amine group, halogen , Cyano group or a combination thereof, R ¹ to R ³ exist independently or two adjacent ones of R ¹ to R ³ are combined to form a ring, and R ⁴ and R ⁵ exist independently or are fused with each other to form a ring.

The first compound includes a dibenzofuran or dibenzothiophene moiety and a nitrogen-containing six-membered ring moiety, and therefore can increase the planarity of the molecular structure while effectively expanding Large LUMO energy band (energy band). Therefore, the first compound may have a structure that easily accepts electrons when an electric field is applied to an organic optoelectronic device manufactured by using the first compound, and therefore, the driving voltage of the organic optoelectronic device may be reduced. In addition, as the LUMO energy band expands, electronic stability will also increase, and thus the life span of the organic photoelectric device can be improved.

For example, two of Z ¹ to Z ³ may be nitrogen.

For example, Z ¹ and Z ² can be nitrogen, and Z ³ can be CR ^a .

For example, Z ² and Z ³ can be nitrogen, and Z ¹ can be CR ^a .

For example, Z ¹ and Z ³ can be nitrogen, and Z ² can be CR ^a .

For example, each of Z ¹ to Z ³ may be nitrogen.

For example, Ar ¹ and Ar ² may independently be hydrogen, deuterium, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, Substituted or unsubstituted naphthyl, substituted or unsubstituted anthryl, substituted or unsubstituted phenanthryl, substituted or unsubstituted terphenylene, substituted or unsubstituted pyridine Group, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted triazinyl, substituted or unsubstituted dibenzothienyl, substituted or unsubstituted dibenzofuranyl, Substituted or unsubstituted carbazolyl, substituted or unsubstituted quinolinyl, substituted or unsubstituted quinolinyl, substituted or unsubstituted isoquinolinyl, substituted or unsubstituted Quinazolinyl, substituted or unsubstituted quinoxolinyl, or a combination thereof.

For example, Ar ¹ and Ar ² may independently be hydrogen, deuterium, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted Or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothienyl, or substituted or unsubstituted stilbene.

For example, Ar ¹ and Ar ² can be independently one of the substituted or unsubstituted groups of group 1.

For example, L ¹ to L ³ may independently be a single bond, substituted or unsubstituted phenylene, substituted or unsubstituted biphenylene, substituted or unsubstituted terphenylene , Substituted or unsubstituted naphthylene, substituted or unsubstituted anthracenyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted dibenzothienyl, substituted or Unsubstituted dibenzofuranyl, substituted or unsubstituted carbazolyl, or substituted or unsubstituted phenylene. For example, L ¹ can be a single bond, substituted or unsubstituted phenylene, substituted or unsubstituted phenylene, substituted or unsubstituted phenylene, substituted Or unsubstituted p-biphenylene or substituted or unsubstituted naphthylene. Here, "substituted" means that at least one hydrogen is replaced by deuterium, C1 to C20 alkyl, C6 to C12 aryl, or cyano.

For example, L ³ may be a single bond.

In an embodiment of the present invention, when L ¹ is a single bond, Ar ¹ is not hydrogen or deuterium, and when L ² is a single bond, Ar ² is not hydrogen or deuterium.

For example, the first compound may be represented by Chemical Formula 1A.

In Chemical Formula 1A, X ¹ , Z ¹ to Z ³ , Ar ¹ , Ar ² , L ² , L ^3, and R ¹ to R ⁵ are the same as described above.

In Chemical Formula 1A, R ^p , R ^q , R ^r and R ^{s are} independently hydrogen, deuterium, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C6 to C30 aryl, A substituted or unsubstituted C3 to C30 heterocyclic group, a substituted or unsubstituted silyl group, a substituted or unsubstituted amine group, a halogen, a cyano group, or a combination thereof, R ^p and R ^q exist independently or They are fused to each other to form a ring, R ^r and R ^s exist independently or are fused to each other to form a ring, and n1 is an integer from 0 to 2.

For example, R ^p , R ^q , R ^r and R ^s may independently be hydrogen, deuterium, substituted or unsubstituted C1 to C4 alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted A substituted biphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted stilbene group, a cyano group, or a combination thereof.

The first compound represented by Chemical Formula 1A includes at least one meta-bonded arylene group, which can inhibit interaction with adjacent molecules and reduce crystallization due to steric hindrance characteristics. ), and thus further improve the efficiency and lifetime characteristics of the organic photoelectric device.

In addition, the first compound includes a kinked moiety (such as a meta-bonded arylene group), and therefore has a higher glass transition temperature (Tg), and can be used in the manufacturing process of organic optoelectronic devices. And/or inhibit the degradation of the first compound during operation, and thus can increase the thermal stability of the first compound.

For example, the first compound may be represented by one of Chemical Formula 1A-1 to Chemical Formula 1A-3, but is not limited to this.

In Chemical Formula 1A-1 to Chemical Formula 1A-3, X ¹ , Z ¹ to Z ³ , Ar ¹ , Ar ² , L ² , L ³ , R ¹ to R ⁵ , R ^p , R ^q , R ^r , R ^s And n1 are the same as described above.

In Chemical Formula 1A-1 to Chemical Formula 1A-3, X ² is O or S, Z ⁴ to Z ^{6 are} independently N or CR ^a , and at least one of Z ⁴ to Z ⁶ is N, R ⁶ to R ¹⁵ Independently hydrogen, deuterium, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C3 to C30 heterocyclic group, substituted or Unsubstituted silyl group, substituted or unsubstituted amine group, halogen, cyano group or a combination thereof, R ⁶ and R ^{7 are} independently present or fused with each other to form a ring, and R ⁹ to R ^{13 are} independently present Or two adjacent ones of R ⁹ to R ¹³ are combined to form a ring.

For example, at least one of Z ⁴ to Z ⁶ may be nitrogen.

For example, two of Z ⁴ to Z ⁶ may be nitrogen.

For example, Z ⁴ and Z ⁵ may be nitrogen, and Z ⁶ may be CR ^a .

For example, Z ⁴ and Z ⁶ can be nitrogen, and Z ⁵ can be CR ^a .

For example, Z ⁵ and Z ⁶ can be nitrogen, and Z ⁴ can be CR ^a .

For example, each of Z ⁴ to Z ⁶ may be nitrogen.

For example, Ar ¹ , Ar ² , R ¹⁴ and R ¹⁵ may independently be hydrogen, deuterium, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted The naphthyl group, substituted or unsubstituted dibenzofuranyl group, substituted or unsubstituted dibenzothienyl group or substituted or unsubstituted stilbene group.

For example, R ^p , R ^q , R ^r and R ^s may independently be hydrogen, deuterium, substituted or unsubstituted C1 to C4 alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted A substituted biphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted stilbene group, a cyano group, or a combination thereof.

The first compound may be, for example, one of the compounds of group 2, but is not limited to this.

The second compound having relatively strong hole characteristics can be represented by a combination of Chemical Formula 2 and Chemical Formula 3.

In Chemical Formula 2 or Chemical Formula 3, Y ¹ and Y ^{2 are} independently a single bond or a substituted or unsubstituted C6 to C30 arylene group, and A ¹ and A ^{2 are} independently substituted or unsubstituted C6 to C30 aryl group, two adjacent * of chemical formula 2 are bonded to two * of chemical formula 3, and the remaining two * of chemical formula 2 are respectively CR ^b and CR ^c , R ²⁰ to R ²³ , R ^b and R ^{c are} independent Ground is hydrogen, deuterium, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C3 to C30 heterocyclic group or a combination thereof, R ²⁰ and R ^{21 are} independently present or fused with each other to form a ring, and R ²² and R ^{23 are} independently present or fused with each other to form a ring.

The second compound may be an indolocarbazole compound substituted with an aryl group, and may have excellent hole characteristics. The second compound is included together with the first compound, and thus can increase the balance between electrons and holes in the light-emitting layer 130 and achieve an organic photoelectric device with a long life.

For example, Y ¹ and Y ² can be independently a single bond, substituted or unsubstituted phenylene, substituted or unsubstituted biphenylene, substituted or unsubstituted terphenylene , Substituted or unsubstituted naphthylene, substituted or unsubstituted anthracenyl, substituted or unsubstituted phenanthrenyl, or substituted or unsubstituted anthrylene.

For example, Y ¹ and Y ² can be independently a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, or a substituted or unsubstituted naphthylene group.

For example, Y ¹ and Y ² can be independently a single bond, substituted or unsubstituted phenylene, substituted or unsubstituted phenylene, substituted or unsubstituted phenylene Phenyl, substituted or unsubstituted p-biphenyl or substituted or unsubstituted naphthylene, where "substituted" means that at least one hydrogen is deuterated, C1 to C20 alkyl, C6 to C12 aromatic Group or cyano substitution.

For example, A ¹ and A ² may independently be substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted Substituted naphthyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted terphenylene, substituted or unsubstituted phenylene, or a combination thereof .

For example, A ¹ and A ² may independently be substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, or substituted or unsubstituted naphthyl.

The second compound may be represented by one of Chemical Formula 2-A to Chemical Formula 2-E depending on the bonding position between Chemical Formula 2 and Chemical Formula 3.

In Chemical Formula 2-A to Chemical Formula 2-E, Y ¹ , Y ² , A ¹ , A ² , R ²⁰ to R ²³ , R ^b and R ^c are the same as described above.

In an embodiment of the present invention, the second compound may be selected from Chemical Formula 2-A or Chemical Formula 2-E according to the driving voltage effect, and may specifically be Chemical Formula 2-A.

The second compound may be, for example, one of the compounds of group 3, but is not limited to this.

In an embodiment of the present invention, the first compound may be represented by Chemical Formula 1A, and the second compound may be represented by Chemical Formula 2-A.

In an embodiment of the present invention, the weight ratio may be about 1:99 to 99:1, for example, about 10:90 to 90:10, about 20:80 to 80:20, about 30:70 to 70:30 , About 40:60 to 60:40 or about 50:50 of the first compound and the second compound.

The host may further include at least one compound other than the first compound and the second compound.

The light emitting layer 130 may further include a dopant. The dopant may be a red dopant, a green dopant, or a blue dopant.

The dopant is mixed with the host in a small amount to cause luminescence, and may generally be an organic compound or a metal complex (such as Al) that emits fluorescence by singlet excitation, or by a ground state Materials that emit light after being excited to a triplet state or more than triplet states (for example, metal complexes). The dopant may be, for example, an inorganic compound, an organic compound, or an organic/inorganic compound, and one or more kinds thereof may be used.

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

[Chemical formula Z] L ₂ MX

In the chemical formula Z, M is a metal, and L and X are the same or different, and are a ligand that forms a complex compound with M.

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

The hole transport auxiliary layer 142 may be disposed between the light emitting layer 130 and the hole transport layer 141 to be described later, and may especially contact the light emitting layer 130. The hole transport auxiliary layer 142 can accurately control hole mobility at the interface between the light emitting layer 130 and the hole transport layer 141 by contacting the light emitting layer 130. Electric hole The transmission auxiliary layer 142 may include multiple layers.

The hole transport auxiliary layer 142 may include, for example, a third compound represented by Chemical Formula 4.

In Chemical Formula 4, L ⁴ to L ^{9 are} independently a single bond, a substituted or unsubstituted C6 to C30 arylene group, a divalent substituted or unsubstituted C2 to C30 heterocyclic group, or a combination thereof, R ⁵⁰ to R ^{55 are} independently hydrogen, deuterium, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C3 to C30 heterocyclic group , Substituted or unsubstituted silyl group, substituted or unsubstituted amine group, halogen, cyano group or a combination thereof, R ⁵⁰ and R ⁵¹ exist independently or are fused with each other to form a ring, R ⁵² and R ⁵³ Exist independently or fused with each other to form a ring, and R ⁵⁴ and R ⁵⁵ exist independently or fused with each other to form a ring.

The third compound has a high HOMO energy level, and therefore has sufficient hole injection characteristics. Therefore, the third compound is applied to the hole transport auxiliary layer 142, and thus can effectively improve the electrical conductivity at the interface between the light emitting layer 130 and the hole transport layer 141. Hole mobility, and effectively reduce the driving voltage of the organic photoelectric device.

For example, L ⁴ to L ⁹ may independently be a single bond, substituted or unsubstituted phenylene, substituted or unsubstituted biphenylene, substituted or unsubstituted terphenylene , Substituted or unsubstituted naphthylene, substituted or unsubstituted anthracenyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted dibenzothienyl, substituted or Unsubstituted dibenzofuranyl, substituted or unsubstituted carbazolyl, or substituted or unsubstituted phenylene. For example, L ⁴ to L ⁹ may independently be a single bond, substituted or unsubstituted phenylene, substituted or unsubstituted phenylene, substituted or unsubstituted phenylene Phenyl, substituted or unsubstituted p-biphenyl or substituted or unsubstituted naphthylene. Here, "substituted" means that at least one hydrogen is replaced by deuterium, C1 to C20 alkyl, C6 to C12 aryl, or cyano.

For example, R ⁵⁰ to R ⁵⁵ may independently be hydrogen, deuterium, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C6 to C30 aryl, or substituted or unsubstituted C3 to C30 heterocyclic group.

For example, R ⁵⁰ to R ⁵⁵ may independently be hydrogen, deuterium, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted Or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothienyl, or substituted or unsubstituted stilbene.

For example, R ⁵⁰ to R ⁵⁵ may be independently substituted or unsubstituted C6 to C30 aryl groups, or, for example, may independently be substituted or unsubstituted phenyl, substituted or unsubstituted bi Phenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthryl, substituted or unsubstituted phenanthryl, substituted or unsubstituted The bis terphenylene or a combination thereof.

For example, at least one of R ⁵⁰ to R ⁵⁵ may be a substituted or unsubstituted C3 to C30 heterocyclic group.

For example, at least one of R ⁵⁰ to R ⁵⁵ may be a group represented by Chemical Formula A.

In Chemical Formula A, X ³ is O or S, R ⁶⁰ to R ^{67 are} independently hydrogen, deuterium, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C6 to C30 aryl, A substituted or unsubstituted C3 to C30 heterocyclic group, a substituted or unsubstituted silyl group, a substituted or unsubstituted amine group, a halogen, a cyano group, or a combination thereof, or a combination of L ⁴ to L ⁴ to A group to which one of L ⁹ is connected, and R ⁶⁰ to R ⁶⁷ exist independently or adjacent two of R ⁶⁰ to R ⁶⁷ are combined to form a ring.

For example, one of R ⁵⁰ to R ⁵⁵ may be a group represented by Chemical Formula A, and the rest of R ⁵⁰ to R ⁵⁵ may independently be a substituted or unsubstituted C6 to C30 aryl group.

For example, two of R ⁵⁰ to R ⁵⁵ may be groups represented by Chemical Formula A, and the rest of R ⁵⁰ to R ⁵⁵ may independently be substituted or unsubstituted C6 to C30 aryl groups.

For example, three of R ⁵⁰ to R ⁵⁵ may be a group represented by Chemical Formula A, and the rest of R ⁵⁰ to R ⁵⁵ may independently be a substituted or unsubstituted C6 to C30 aryl group.

The third compound may be, for example, one of the compounds of group 4, but is not limited to this.

The hole transport layer 141 is disposed between the anode 110 and the light-emitting layer 130, and can help holes to be easily transmitted from the anode 110 to the light-emitting 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 Chemical Formula 5, but it is not limited thereto.

In Chemical Formula 5, R ¹¹⁸ to R ^{121 are} independently hydrogen, deuterium, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C2 to C30 heterocyclic group or a combination thereof, R ¹¹⁸ and R ^{119 are} independently present or fused with each other to form a ring, R ¹²⁰ and R ^{121 are} independently present or fused with each other to form a ring, Ar ¹⁰ to Ar ^{12 are} independently A substituted or unsubstituted C6 to C30 aryl group or a substituted or unsubstituted C2 to C30 heterocyclic group, and L ¹⁰ to L ^{13 are} independently a single bond, a substituted or unsubstituted C6 to C30 extension Aryl, a divalent substituted or unsubstituted C2 to C30 heterocyclic group, or a combination thereof.

For example, Ar ¹⁰ may be a substituted or unsubstituted C6 to C30 aryl group, and for example, Ar ¹⁰ may be a substituted or unsubstituted phenyl group or a substituted or unsubstituted biphenyl group.

For example, Ar ¹¹ and Ar ¹² may independently be substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted stilbene, substituted or unsubstituted Bis-phenylene group, substituted or unsubstituted terphenylene group, substituted or unsubstituted anthryl group, substituted or unsubstituted terphenyl group, substituted or unsubstituted dibenzofuran Group, substituted or unsubstituted dibenzothienyl or a combination thereof.

The compound represented by Chemical Formula 5 may be, for example, one of the compounds of Group 5, but is not limited to this.

In addition to the light-emitting layer 130, the hole transport auxiliary layer 142, and the hole transport layer 141, the organic layer 105 may further include a hole injection layer, an electron blocking layer, an electron transport layer, an electron injection layer and/or a hole blocking layer ( Not shown in the figure).

The organic light emitting diode 300 can be manufactured by forming an anode or a cathode on a substrate, using, for example, evaporation, sputtering, plasma plating, and ion plating. The organic layer is formed by a dry film forming method such as plating) or a solution process, and a cathode or an anode is formed on the organic layer.

Organic photoelectric devices can be applied to display devices. For example, organic light emitting diodes can be applied to organic light emitting diode (OLED) displays.

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

Synthesis example

Synthesis Example 1: Synthesis of Compound B-24

a) Synthesis of intermediate B-24-1

Dissolve 15 g (81.34 millimoles) of cyanuric chloride in 200 ml of anhydrous tetrahydrofuran in a 500 ml round bottom flask, and add 1 equivalent of cyanuric chloride dropwise to it at 0°C under a nitrogen atmosphere. 4-biphenylmagnesium bromide solution (0.5M tetrahydrofuran), and the mixture was slowly warmed to room temperature. The reaction solution was stirred at room temperature for 1 hour, and 500 ml of ice water was added thereto to separate the layers. The organic layer was separated therefrom, treated with anhydrous magnesium sulfate, and concentrated. The concentrated residue was recrystallized with tetrahydrofuran and methanol to obtain 17.2 g of intermediate B-24-1.

b) Synthesis of intermediate B-24-2

17.2 g (56.9 millimoles) of intermediate B-24-1 was added to 200 ml of tetrahydrofuran and 100 ml of distilled water in a 500 ml round bottom flask, and added to it Added 2 equivalents of dibenzofuran-3-boronic acid (Chemical Abstracts Service (Chemical Abstracts Service, cas): 395087-89-5), 0.03 equivalents of tetrakistriphenylphosphine palladium (tetrakistriphenylphosphine palladium) and 2 equivalents The mixture was heated and refluxed under a nitrogen atmosphere. After 18 hours, the reaction solution was cooled, and the solid precipitated therein was filtered and washed with 500 ml of water. The solid was recrystallized with 500 ml of monochlorobenzene to obtain 13.05 g of intermediate B-24-2.

c) Synthesis of compound B-24

According to the same method as b), compound B-24 was synthesized using intermediate B-24-2 and 1.1 equivalents of B-[1,1':4',1"-terphenyl]-3-ylboronic acid.

Calculated by liquid chromatography (LC)/mass spectrum (MS): C ₄₅ H ₂₉ N ₃ O accurate mass: 627.2311 experimental value 628.24 [M+H]

Synthesis Example 2: Synthesis of Compound B-71

[Reaction Scheme 2]

a) Synthesis of intermediate B-71-1

Put 14.06 g (56.90 millimoles) of 3-bromo-dibenzofuran, 200 ml of tetrahydrofuran and 100 ml of distilled water into a 500 ml round bottom flask, and add 1 equivalent of 3'-chloro-phenylboronic acid, 0.03 The equivalent of tetrakis-triphenylphosphine palladium and 2 equivalents of potassium carbonate, and the mixture was heated and refluxed under a nitrogen atmosphere. After 18 hours, the reaction solution was cooled, and the solid precipitated therein was filtered and washed with 500 ml of water. The solid was recrystallized with 500 ml of monochlorobenzene to obtain 12.05 g of intermediate B-71-1. (The yield is 76%)

b) Synthesis of intermediate B-71-2

Put 24:53 g (88.02 millimoles) of intermediate B-71-1 and 250 ml of dimethylformamide (DMF) into a 500 ml round bottom flask, and add 0.05 equivalent of dichlorobis Phenylphosphinoferrocene palladium (dichlorodiphenylphosphinoferrocene palladium), 1.2 equivalent dual frequency Bispinacolato diboron and 2 equivalents of potassium acetate, and the mixture was heated and refluxed under a nitrogen atmosphere for 18 hours. The reaction solution was cooled and added dropwise to 1 liter of water. The solid obtained therefrom was dissolved in boiling toluene, treated with activated carbon, and filtered through silica gel, and the filtrate obtained therefrom was concentrated. The concentrated solid was stirred with a small amount of hexane, and filtered to obtain 22.81 g of intermediate B-71-2. (The yield is 70%)

c) Synthesis of compound B-71

According to the same method as Synthesis Example a), by using the intermediates B-71-2 and 2,4-bis([1,1'-biphenyl]-4-yl)- Compound B-71 was synthesized from 6-chloro-1,3,5-triazine.

LC/MS calculated: C ₄₅ H ₂₉ N ₃ O Accurate mass: 627.2311 experimental value 628.25[M+H]

Synthesis Example 3: Synthesis of Compound B-20

a) Synthesis of intermediate B-20-1

Put 22.6 grams (100 millimoles) of 2,4-dichloro-6-phenyltriazine together with 100 milliliters of tetrahydrofuran, 100 milliliters of toluene and 100 milliliters of distilled water into a 500 milliliter round bottom flask, and add 0.9 equivalent of Dibenzofuran-3-boronic acid (CAS number: 395087-89-5), 0.03 equivalents of tetrakis-triphenylphosphine palladium and 2 equivalents of potassium carbonate, and the mixture was heated and refluxed under a nitrogen atmosphere. After 6 hours, the reaction solution was cooled, and the organic layer obtained after removing the water layer was dried under reduced pressure. The solid obtained therefrom was washed with water and hexane, and recrystallized with 200 ml of toluene to obtain 21.4 g of intermediate B-20-1 (yield 60%).

b) Synthesis of compound B-20

According to the same method as b) of Synthesis Example 3, intermediate B-20-1 and 1.1 equivalents of (5'-phenyl[1,1': 3',1"-terphenyl]-4-yl) were used -Boric acid (CAS number: 491612-72-7) to synthesize compound B-20.

Calculated by LC/MS: C ₄₅ H ₂₉ N ₃ O Accurate mass: 627.2311 experimental value 628.24[M+H]

Synthesis Example 4: Synthesis of Compound B-124

a) Synthesis of intermediate B-124-1

According to b) of Synthesis Example 1, intermediate B-124-1 was synthesized using 1-bromo-3-chloro-5-phenylbenzene and 1.1 equivalents of biphenyl-4-boronic acid. Here, the product obtained therefrom was purified through a flash column with hexane instead of recrystallization.

b) Synthesis of intermediate B-124-2

30 g (88.02 millimoles) of intermediate B-124-1 was added to 250 ml of dimethylformamide in a 500 ml round bottom flask, and 0.05 equivalent of dichlorodiphenylphosphino dicene was added to it Iron palladium), 1.2 equivalents of bispinacol diboron and 2 equivalents of potassium acetate, and the mixture was heated and refluxed under a nitrogen atmosphere for 18 hours. The reaction solution was cooled and added dropwise to 1 liter of water to obtain a solid. The solid was dissolved in boiling toluene, treated with activated carbon, filtered through silica gel, and the filtrate was concentrated. The concentrated solid was stirred with a small amount of hexane and filtered to obtain 28.5 g of intermediate B-124-2 (70% yield).

c) Synthesis of compound B-124

According to the same method as b) of Synthesis Example 3, compound B-124 was synthesized using 1.0 equivalent of Intermediate B-124-2 and Intermediate B-17-1.

Calculated by LC/MS: C ₄₅ H ₂₉ N ₃ O Accurate mass: 627.2311 experimental value 628.22[M+H]

Synthesis Example 5: Synthesis of Compound B-3

a) Synthesis of intermediate B-3-1

Stir magnesium (7.86 g, 323 millimoles) and iodine (1.64 grams, 6.46 millimoles) with 0.1 liter of tetrahydrofuran (THF) under nitrogen atmosphere for 30 minutes, and slowly add them at 0°C for more than 30 minutes 1-bromo-3,5-diphenylbenzene (100 g, 323 millimoles) dissolved in 0.3 liters of tetrahydrofuran was added dropwise. The obtained mixed solution was slowly added dropwise to 64.5 g (350 millimoles) of cyanuric chloride solution dissolved in 0.5 liter of tetrahydrofuran at 0° C. for 30 minutes. When the reaction was completed, water was added to the reaction solution, and an extract was obtained with dichloromethane (DCM), filtered after removing water therefrom with anhydrous MgSO ₄ , and concentrated under reduced pressure. The residue obtained therefrom was separated via flash column chromatography to obtain intermediate B-3-1 (79.4 g, 65%).

b) Synthesis of compound B-3

According to the same method as in b) of Synthesis Example 1, compound B-3 was synthesized using intermediate B-3-1.

LC/MS calculated: C ₄₅ H ₂₇ N ₃ O ₂ Accurate mass: 641.2103 experimental value 642.21[M+H]

Synthesis Example 6: Synthesis of Compound HC-28

a) Synthesis of intermediate HC-28-1

Intermediate A (30 g, 121.9 millimoles), 1 equivalent of 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bis(1, 3,2-dioxaborolane)(4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane) ), 2 when The amount of potassium acetate, 0.03 equivalent of 1,1'-bis(diphenylphosphino)ferrocene-palladium dichloride (II) and 0.2 equivalent of tricyclohexylphosphine were added to 300 ml of N in a 500 ml flask , N-dimethylformamide, and the mixture was stirred at 130°C for 12 hours. When the reaction is complete, the reaction solution is extracted with water and EA to obtain an organic layer, and after removing water therefrom with magnesium sulfate, the organic layer is concentrated, and then purified by column chromatography to obtain a white solid intermediate HC-28-1 (29.66 g, 83% yield).

b) Synthesis of intermediate HC-28-2

Combine 29.66 grams (0.4 mol) of intermediate HC-28-1, 2 equivalents of intermediate B (1-bromo-20 nitrobenzene), 2 equivalents of potassium carbonate and 0.02 equivalents of tetrakis(triphenylphosphine) palladium (0) Add 200 ml of 1,4-dioxane and 100 ml of water in a 500 ml flask, and heat the mixture at 90° C. under a stream of nitrogen for 16 hours. After removing the reaction solvent from it, the product obtained therefrom was dissolved in dichloromethane, filtered through silica gel/celite, and after removing an appropriate amount of organic solvent from it, recrystallized with methanol, To obtain solid intermediate HC-28-2 (16.92 g, yield 58%).

c) Synthesis of intermediate HC-28-3

8.7 grams (30.2 millimoles) of intermediate HC-28-2, 7.5 grams (36.2 millimoles) of intermediate C (2-bromonaphthalene), 4.3 grams (45.3 millimoles) of sodium tertiary butoxide (NaOtBu ), 1.0 g (1.8 millimoles) of Pd(dba) ₂ and 2.2 g of tri-tertiary butyl phosphine (P(tBu) ₃ ) (50% in toluene) were added to 150 ml of xylene in a 500 ml flask And the mixture was heated and refluxed under a stream of nitrogen for 12 hours. After the xylene was removed, 200 ml of methanol was added to the mixture obtained therefrom to crystallize the solid, and the solid was filtered, dissolved in dichloromethane, filtered through silica gel/celite, and After removing an appropriate amount of organic solvent, it was recrystallized with acetone to obtain intermediate HC-28-3 (9.83 g, yield 77%).

d) Synthesis of intermediate HC-28-4

Put the intermediate HC-28-3 (211.37 g, 0.51 mol) and triethyl phosphite (528 ml, 3.08 mol) into a 1000 ml flask, and after nitrogen replacement, the mixture Stir at 160°C for 12 hours. When the reaction was completed, 3 liters of MeOH was added thereto, and the obtained mixture was stirred and filtered, and the filtrate was volatilized. The residue was purified by column chromatography with hexane to obtain intermediate HC-28-4 (152.14 g, yield 78%).

e) Synthesis of compound HC-28

According to the same method as in Synthesis Example c), the compound HC-28 was synthesized using the intermediate HC-28-4 and the intermediate HC-28-B.

Synthesis Example 7: Synthesis of Compound HC-18

[Reaction Scheme 8]

a) Synthesis of intermediate HC-18-1

According to the same method as c) of Synthesis Example 9, using 4-bromobiphenyl as an intermediate instead of 2-bromonaphthalene, intermediate HC-18-1 was synthesized.

b) Synthesis of intermediate HC-18-2

According to the same method as d) of Synthesis Example 9, the intermediate HC-18-2 was synthesized.

c) Synthesis of intermediate HC-18-3

According to the same method as b) of Synthesis Example 1, intermediate HC-18-A and intermediate HC-18-B were used to synthesize intermediate HC-18-3.

d) Synthesis of compound HC-18

According to the same method as e) of Synthesis Example 9, compound HC-18 was synthesized using intermediate HC-18-2 and intermediate HC-18-3.

Synthesis Example 8: Synthesis of Compound HC-20

a) Synthesis of intermediate HC-20-1

According to the same method as b) of Synthesis Example 1, intermediate HC-20-A and intermediate HC-20-B were used to synthesize intermediate HC-20-1.

b) Synthesis of compound HC-20

According to the same method as e) of Synthesis Example 9, compound HC-20 was synthesized using intermediate HC-18-2 and intermediate HC-20-1.

Synthesis Example 9: Synthesis of Compound HC-37

[Reaction Scheme 13]

According to the same method as e) of Synthesis Example 9, compound HC-37 was synthesized using intermediate HC-28-4 and intermediate HC-18-3.

Synthesis Example 10: Synthesis of Compound C-14

8 g (31.2 millimoles) of intermediate I-1, 20.5 grams (73.32 millimoles) 4-iodobiphenyl (4-iodobiphenyl), 1.19 grams (6.24 millimoles) CuI, 1.12 grams (6.24 millimoles) Millimoles) 1,10-phenanthroline (1,10-phenanthroline) and 12.9 grams (93.6 millimoles) K ₂ CO _{3 were} put into a round bottom flask, 50 milliliters of DMF was added thereto, and the mixture was placed in a nitrogen atmosphere Reflux and stir for 24 hours. When the reaction was completed, distilled water was added to precipitate the solid, and the solid was filtered. The solid was dissolved in 250 ml of xylene and filtered through silica gel to precipitate a white solid, thereby obtaining 16.2 g of compound C-14 (93% yield).

Synthesis Example 11: Synthesis of Compound F-148

Compound F-148 was synthesized with reference to Korean Registered Patent No. 10-1627746.

Comparative Synthesis Example 1 and Comparative Synthesis Example 2

With reference to Korean Patent Publication No. 10-2016-0149527, compound Ref. 1 and compound Ref. 2 were synthesized respectively.

Manufacturing organic light-emitting diodes

Example 1

The glass substrate coated with indium tin oxide (ITO) as a 1500 angstrom (Å) thick film was washed with distilled water. After washing with distilled water, the glass substrate is ultrasonic wave-washed and dried using solvents such as isopropanol, acetone, methanol, etc., and then moved to a plasma cleaner, where oxygen plasma is used Clean for 10 minutes and move to vacuum depositor. Using the obtained ITO transparent electrode as an anode, compound A was vacuum deposited on an ITO substrate to form a 700 angstrom hole injection layer, compound B was deposited on the injection layer to a thickness of 50 angstrom, and the compound C is deposited to a thickness of 700 angstroms to form a hole transport layer. The compound F-148 synthesized in Synthesis Example 11 was deposited on the hole transport layer to form a 400 angstrom thick hole transport auxiliary layer. By simultaneously vacuum depositing the compound B-24 synthesized in Synthesis Example 1 and the compound HC-28 synthesized in Synthesis Example 6 as the main body and 2% by weight of [Ir(piq) ₂ acac] as the dopant, A 400 angstrom thick light-emitting layer is formed on the hole transport auxiliary layer. Here, compound B-24 and compound HC-28 are used in a weight ratio of 3:7. Subsequently, compound D and Liq were simultaneously vacuum-deposited on the light-emitting layer at a ratio of 1:1 to form an electron transport layer with a thickness of 300 angstroms, and the Liq was vacuum deposited on the electron transport layer to a thickness of 15 angstroms and Al was vacuum deposited to a thickness of 1200 angstroms to form a cathode, thereby manufacturing an organic light-emitting diode.

The organic light emitting diode has a six-layer organic thin structure, and specifically has the following structure.

ITO/compound A (700 angstroms)/compound B (50 angstroms)/compound C (700 angstroms)/compound F-148 (400 angstroms)/EML [Compound B-24: HC-28: [Ir(piq) ₂ acac ] (2% by weight)] (400 angstroms)/compound D: Liq (300 angstroms)/Liq (15 angstroms)/Al (1200 angstroms).

Compound A: N4,N4'-Diphenyl-N4,N4'-bis(9-phenyl-9H-carbazol-3-yl)biphenyl-4,4'-diamine (N4,N4'- diphenyl-N4,N4'-bis(9-phenyl-9H-carbazol-3-yl)biphenyl-4,4'-diamine)

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

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

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

Example 2 to Example 9 and Comparative Example 1 to Comparative Example 6

Except that each compound shown in Table 1 was used instead of Compound B-24 and Compound HC-28 as the host of the light-emitting layer and each compound shown in Table 1 was used instead of Compound F-148 of the hole transport auxiliary layer, according to Example 1 The same method is used to manufacture organic light-emitting diodes.

Evaluation

The driving voltage and power efficiency of the organic light emitting diodes according to Examples 1 to 9 and Comparative Examples 1 to 6 were measured.

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

(1) Measure the driving voltage

A current-voltage meter (Keithley 2400) was used to measure the driving voltage of each diode to obtain the result.

(2) The measurement depends on the current density change of the voltage change

Regarding the value of current flowing in the unit device, a current-voltmeter (Keithley 2400) was used to measure the obtained organic light-emitting diode when the voltage increased from 0 volts to 10 volts, and the measured current Divide the value by the area to get the result.

(3) The measurement depends on the brightness change of the voltage change

A luminance meter (Minolta Cs-1000A) was used to measure the luminance when the voltage of the organic light-emitting diode increased from 0 volts to 10 volts.

(4) Measuring power efficiency

Calculate the power efficiency (lm/w) using the brightness, current density and voltage measured in (2) and (3).

Referring to Table 1, compared to the organic light emitting diodes according to Comparative Examples 1 to 6, the organic light emitting diodes according to Examples 1 to 9 show significantly lower driving voltage and significantly improved power efficiency.

Although the present invention has been described in conjunction with exemplary embodiments currently regarded as practical, it should be understood that the present invention is not limited to the disclosed embodiments, but instead is intended to cover the spirit and scope included in the scope of the appended patent Various retouching and equivalent configurations.

105‧‧‧Organic layer

110‧‧‧Anode

120‧‧‧Cathode

130‧‧‧Light-emitting layer

141‧‧‧Hole Transmission Layer

142‧‧‧hole transmission auxiliary layer

300‧‧‧Organic Light Emitting Diode

Claims (15)

An organic photoelectric device, comprising: an anode and a cathode facing each other, a light-emitting layer, a hole transport layer, a hole transport layer, and a hole between the anode and the light-emitting layer. A transport auxiliary layer is provided between the light-emitting layer and the hole transport layer, wherein the light-emitting layer includes a first compound represented by Chemical Formula 1 and a second compound represented by a combination of Chemical Formula 2 and Chemical Formula 3, and The hole transport auxiliary layer includes a third compound represented by Chemical Formula 4:

Wherein, in Chemical Formula 1, X ¹ is O or S, Z ¹ to Z ^{3 are} independently N or CR ^a , at least two of Z ¹ to Z ³ are N, Ar ¹ and Ar ^{2 are} independently hydrogen, A substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heterocyclic group or a combination thereof, L ¹ to L ^{3 are} independently a single bond, a substituted or unsubstituted C6 to C30 aryl group, divalent substituted or unsubstituted C2 to C30 heterocyclic group or a combination thereof, R ¹ to R ⁵ and R ^{a are} independently hydrogen, deuterium, substituted or unsubstituted C1 to C20 alkane Group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C3 to C30 heterocyclic group, substituted or unsubstituted silyl group, substituted or unsubstituted amine group, halogen , Cyano group or a combination thereof, R ¹ to R ^{3 are} independently present or two adjacent ones of R ¹ to R ³ are combined to form a ring, and R ⁴ and R ^{5 are} independently present or fused with each other to form a ring,

Wherein, in Chemical Formula 2 or Chemical Formula 3, Y ¹ and Y ^{2 are} independently a single bond or a substituted or unsubstituted C6 to C30 arylene group, and A ¹ and A ^{2 are} independently substituted or unsubstituted C6 to C30 aryl groups, two adjacent * of formula 2 are bonded to two * of formula 3, and the remaining two * of formula 2 are CR ^b and CR ^c , R ²⁰ to R ²³ , R ^b and R ^{c is} independently hydrogen, deuterium, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C3 to C30 heterocyclic group or a combination thereof , R ²⁰ and R ^{21 are} independently present or fused with each other to form a ring, and R ²² and R ^{23 are} independently present or fused with each other to form a ring,

Wherein, in the chemical formula 4, L ⁴ to L ^{9 are} independently a single bond, a substituted or unsubstituted C6 to C30 arylene group, a divalent substituted or unsubstituted C2 to C30 heterocyclic group, or a combination thereof , R ⁵⁰ to R ^{55 are} independently hydrogen, deuterium, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted dibenzofuran Group, substituted or unsubstituted dibenzothienyl group, substituted or unsubstituted silyl group, substituted or unsubstituted amine group, halogen, cyano or a combination thereof, R ⁵⁰ and R ^{51 are} independently Exist or fused with each other to form a ring, R ⁵² and R ⁵³ exist independently or fused with each other to form a ring, and R ⁵⁴ and R ⁵⁵ exist independently or fused with each other to form a ring. The organic optoelectronic device according to the first item of the scope of patent application, wherein Ar ¹ and Ar ^{2 of} Chemical Formula 1 are independently hydrogen, deuterium, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl , Substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthryl, substituted or unsubstituted phenanthryl, substituted or unsubstituted biphenyl Terphenylene, substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted triazinyl, substituted or unsubstituted dibenzothienyl, Substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted quinolinyl, substituted or unsubstituted quinolinyl, substituted or unsubstituted The isoquinolinyl group, the substituted or unsubstituted quinazolinyl group, the substituted or unsubstituted quinoxolinyl group, or a combination thereof. The organic optoelectronic device according to the first item of the patent application, wherein Ar ¹ and Ar ^{2 of} Chemical Formula 1 are independently one of the substituted or unsubstituted groups listed in Group 1:

The organic optoelectronic device as described in item 1 of the scope of patent application, wherein the first compound is represented by Chemical Formula 1A: [Chemical Formula 1A]

Wherein, in the chemical formula 1A, X ¹ is O or S, Z ¹ to Z ^{3 are} independently N or CR ^a , at least two of Z ¹ to Z ³ are N, Ar ¹ and Ar ^{2 are} independently hydrogen, Deuterium, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C2 to C30 heterocyclic group, or a combination thereof, L ² and L ^{3 are} independently single bonds, substituted or unsubstituted C6 to C30 arylene group, a divalent C2 to C30 via a substituted or unsubstituted heterocyclic group or a combination thereof, R ¹ to ^{R 5, R a, R p} , R q, R r and R ^s are independently hydrogen , Deuterium, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C3 to C30 heterocyclic group, substituted or unsubstituted Silyl group, substituted or unsubstituted amine group, halogen, cyano group or a combination thereof, R ¹ to R ³ exist independently or adjacent two of R ¹ to R ³ are combined to form a ring, R ⁴ and R ⁵ exists independently or fused with each other to form a ring, R ^p and R ^q exist independently or fused with each other to form a ring, R ^r and R ^s exist independently or fused with each other to form a ring, and n1 is 0 to An integer of 2. The organic photoelectric device according to item 4 of the scope of patent application, wherein the first compound is represented by one of Chemical Formula 1A-1 to Chemical Formula 1A-3:

Wherein, in Chemical Formula 1A-1 to Chemical Formula 1A-3, X ¹ and X ^{2 are} independently O or S, Z ¹ to Z ^{6 are} independently N or CR ^a , and at least two of Z ¹ to Z ³ are At least one of N, Z ⁴ to Z ⁶ is N, Ar ¹ and Ar ^{2 are} independently hydrogen, deuterium, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C2 to C30 Heterocyclic group or a combination thereof, L ² and L ^{3 are} independently a single bond, a substituted or unsubstituted C6 to C30 arylene group, a divalent substituted or unsubstituted C2 to C30 heterocyclic group or a combination thereof , R ¹ to R ¹⁵ , R ^a , R ^p , R ^q , R ^r and R ^{s are} independently hydrogen, deuterium, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C3 to C30 heterocyclic group, substituted or unsubstituted silyl group, substituted or unsubstituted amine group, halogen, cyano group or a combination thereof, R ¹ to R ³ exists independently or two adjacent ones of R ¹ to R ³ are combined to form a ring, R ⁴ and R ⁵ exist independently or are fused with each other to form a ring, R ⁶ and R ⁷ exist independently or are fused with each other To form a ring, R ⁹ to R ¹³ exist independently or adjacent two of R ⁹ to R ¹³ are combined to form a ring, R ^p and R ^q exist independently or are fused with each other to form a ring, R ^r and R ^s exist independently or are fused with each other to form a ring, and n1 is an integer from 0 to 2. The organic optoelectronic device according to item 5 of the scope of patent application, wherein Ar ¹ , Ar ² , R ¹⁴ and R ^{15 are} independently hydrogen, deuterium, substituted or unsubstituted phenyl, substituted or unsubstituted Biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothienyl, or substituted or unsubstituted stilbene, And R ^p , R ^q , R ^r and R ^{s are} independently hydrogen, deuterium, substituted or unsubstituted C1 to C4 alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted bi Phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted terphenyl, substituted or unsubstituted stilbene, cyano, or a combination thereof. The organic optoelectronic device according to item 1 of the scope of patent application, wherein the second compound is represented by one of Chemical Formula 2-A to Chemical Formula 2-E:

Wherein, in Chemical Formula 2-A to Chemical Formula 2-E, Y ¹ and Y ^{2 are} independently a single bond or a substituted or unsubstituted C6 to C30 arylene group, and A ¹ and A ^{2 are} independently substituted or Unsubstituted C6 to C30 aryl group, R ²⁰ to R ²³ , R ^b and R ^{c are} independently hydrogen, deuterium, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C3 to C30 heterocyclic group or a combination thereof, R ²⁰ and R ²¹ independently exist or are mutually fused to form a ring, and R ²² and R ²³ independently exist or are mutually fused To form a ring. The organic optoelectronic device as described in item 1 of the patent application, wherein Y ¹ and Y ^{2 are} independently a single bond, substituted or unsubstituted phenylene, substituted or unsubstituted biphenylene, or A substituted or unsubstituted naphthylene group, and A ¹ and A ^{2 are} independently substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl , Substituted or unsubstituted naphthyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted phenylene, substituted or unsubstituted的茀基 or a combination thereof. The organic optoelectronic device according to the first item of the patent application, wherein R ⁵⁰ to R ^{55 of the} chemical formula 4 are independently hydrogen, deuterium, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl , Substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthryl, substituted or unsubstituted phenanthryl, substituted or unsubstituted biphenyl Triphenylene, substituted or unsubstituted dibenzothienyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted chrysene基 or a combination thereof. The organic optoelectronic device as described in item 1 of the patent application, wherein R ⁵⁰ to R ^{55 of} Chemical Formula 4 are independently substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or Unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted phenylene Or a combination. The organic photoelectric device according to the first item of the patent application, wherein at least one of R ⁵⁰ to R ⁵⁵ of Chemical Formula 4 is a group represented by Chemical Formula A: [Chemical Formula A]

Wherein, in the chemical formula A, X ³ is O or S, R ⁶⁰ to R ^{67 are} independently hydrogen, deuterium, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C6 to C30 aryl Group, substituted or unsubstituted C3 to C30 heterocyclic group, substituted or unsubstituted silyl group, substituted or unsubstituted amine group, halogen, cyano group or a combination thereof, or in combination with L of Chemical Formula 4 A group to which one of ⁴ to L ⁹ is connected, and R ⁶⁰ to R ⁶⁷ exist independently or adjacent two of R ⁶⁰ to R ⁶⁷ are combined to form a ring. The organic photoelectric device according to claim 1, wherein the hole transport auxiliary layer contacts the light-emitting layer. The organic photoelectric device as described in claim 1, wherein the hole transport layer contains a compound represented by Chemical Formula 5: [Chemical Formula 5]

Wherein, in chemical formula 5, R ¹¹⁸ to R ^{121 are} independently hydrogen, deuterium, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted A substituted C2 to C30 heterocyclic group or a combination thereof, R ¹¹⁸ and R ^{119 are} independently present or fused with each other to form a ring, R ¹²⁰ and R ^{121 are} independently present or fused with each other to form a ring, Ar ¹⁰ to Ar ^{12 are} independent Ground is a substituted or unsubstituted C6 to C30 aryl group or a substituted or unsubstituted C2 to C30 heterocyclic group, and L ¹⁰ to L ^{13 are} independently a single bond, a substituted or unsubstituted C6 to C30 arylene group, divalent substituted or unsubstituted C2 to C30 heterocyclic group or a combination thereof. The organic optoelectronic device according to item 13 of the scope of patent application, wherein Ar ¹⁰ of Chemical Formula 5 is a substituted or unsubstituted phenyl group or a substituted or unsubstituted biphenyl group, and Ar ¹¹ and Ar of Chemical Formula 5 ^{12 is} independently substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted phosphonium, substituted or unsubstituted bisphosphonium, substituted or unsubstituted Substituted terphenylene, substituted or unsubstituted anthracenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted Dibenzothienyl or a combination thereof. A display device includes the organic photoelectric device as described in any one of items 1 to 14 in the scope of the patent application.

Images