TW201920603A - 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 photovoltaic devices (organic photovoltaic diodes) are devices that convert electrical energy into light energy and vice versa.

Organic photovoltaic devices can be classified as follows based on their driving principles. One is a photovoltaic device, where exciton is generated by light energy, the exciton is separated into electrons and holes and transferred to different electrodes to generate electricity, and the other is a light emitting device, in which a voltage or current is supplied to the electrode to Electrical energy produces light energy.

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

Among them, organic light emitting diodes (organic light emitting diodes, OLEDs) have recently attracted attention due to the increased demand for flat panel displays. The organic light emitting diode converts electric energy into light by applying a 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 photovoltaic device capable of improving power efficiency by reducing a driving voltage.

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

According to an embodiment, an organic photovoltaic device includes: an anode and a cathode facing each other; a light-emitting layer provided between the anode and the cathode; and a hole transport layer provided 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.

[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, Ar ¹ and Ar ^{2 are} independently hydrogen, and are substituted Or unsubstituted C6 to C30 aryl, substituted or unsubstituted C2 to C30 heterocyclyl, or a combination thereof, L ¹ to L ^{3 are} independently a single bond, substituted or unsubstituted C6 to C30 Aryl, divalent substituted or unsubstituted C2 to C30 heterocyclyl, or a combination thereof, R ¹ to R ⁵ and R ^{a are} independently hydrogen, deuterium, substituted or unsubstituted C1 to C20 alkyl, Substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C3 to C30 heterocyclyl, substituted or unsubstituted silyl, substituted or unsubstituted amine, halogen, cyanide 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, and R ⁴ and R ⁵ independently exist or are fused to each other to form a ring, [Chemical formula 2] [Chemical Formula 3] Among them, 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 * in Chemical Formula 2 are bonded to two * in Chemical Formula 3, and the remaining two * in Chemical 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 heterocyclyl, or a combination thereof , R ²⁰ and R ²¹ independently exist or are fused with each other to form a ring, and R ²² and R ²³ independently exist or are fused with each other to form a ring, [Chemical Formula 4] Among them, in Chemical Formula 4, L ⁴ to L ^{9 are} independently a single bond, a substituted or unsubstituted C6 to C30 aryl 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 A cyclic group, a substituted or unsubstituted silane group, a substituted or unsubstituted amine group, a halogen, a cyano group, or a combination thereof, R ⁵⁰ and R ⁵¹ independently exist or are fused with each other to form a ring, R ⁵² and R ^{53 is} independently present or fused to each other to form a ring, and R ⁵⁴ and R ^{55 are} independently existed or fused to each other to form a ring.

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

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

Hereinafter, embodiments of the present invention will be 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 scope.

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

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

In this specification, when a definition is not otherwise provided, "hetero" means that one to three heteroatoms selected from N, O, S, P, and Si are contained in one functional group and the remainder is 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 a p-orbital domain that forms a conjugate, such as phenyl, naphthyl, etc., two or More hydrocarbon aromatic moieties may be connected by a sigma bond, and may be, for example, biphenyl, terphenyl, tetraphenyl, etc., and two or more hydrocarbon aromatic moieties are fused directly or indirectly (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, "heterocyclyl" is a general concept of heteroaryl, and may include at least one heteroatom selected from N, O, S, P, and Si instead of a cyclic compound (for example, aryl, cycloalkyl, (Fused ring or combination thereof). When the heterocyclyl is a fused ring, the entire ring or each ring of the heterocyclyl may contain one or more heteroatoms.

For example, "heteroaryl" may refer to an aryl group containing at least one heteroatom selected from N, O, S, P, and Si instead of carbon (C). Two or more heteroaryl groups are directly connected through a sigma bond, or when a 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, quinolinyl, isoquinolinyl, and the like.

More specifically, the substituted or unsubstituted C6 to C30 aryl and / or the substituted or unsubstituted C2 to C30 heterocyclyl may be a substituted or unsubstituted phenyl, a substituted or unsubstituted Substituted naphthyl, substituted or unsubstituted anthryl, substituted or unsubstituted phenanthryl, substituted or unsubstituted naphthacenyl group, substituted or unsubstituted fluorenyl (Pyrenyl group), substituted or unsubstituted biphenyls, substituted or unsubstituted p-terphenyls, substituted or unsubstituted m-terphenyls, substituted or unsubstituted ortho-terphenyls , Substituted or unsubstituted chrysenyl group, substituted or unsubstituted triphenylene, substituted or unsubstituted perylenyl group, substituted or unsubstituted Fluorenyl, 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 oxadiazolyl, substituted or unsubstituted Thiadiazolyl, substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted pyrazinyl, substituted or unsubstituted triazinyl, substituted Or unsubstituted benzofuranyl, substituted or unsubstituted benzothienyl, substituted or unsubstituted benzimidazolyl, substituted or unsubstituted indolyl, substituted or unsubstituted Substituted quinolinyl, substituted or unsubstituted isoquinolinyl, substituted or unsubstituted quinazolinyl, substituted or unsubstituted quinoxalinyl, substituted or unsubstituted naphthalene Pyridyl, substituted or unsubstituted benzoxazinyl, substituted or unsubstituted benzothiazinyl, substituted or unsubstituted acridinyl group, substituted or unsubstituted Phenazinyl, substituted or unsubstituted phenothiazinyl, substituted or unsubstituted phenoxazine Group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted dibenzothiophenyl group, or a combination thereof, but is not limited thereto.

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

In addition, electronic characteristics refer to the ability to accept electrons when an electric field is applied, and because of 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 The electrons formed in the light emitting layer can be easily transferred into the cathode and transferred in the light emitting layer.

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

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

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

In the drawings, the thicknesses of layers, films, plates, regions, etc. are exaggerated for clarity. Throughout the description, the same reference numbers designate the same components. It will be understood that when an element (eg, layer, film, region, or substrate) is referred to as being “on” another element, it can be directly on the other element or intervening elements may also be present. In contrast, when an element is referred to as being "directly on" another element, there are no intervening elements present.

FIG. 1 is a schematic cross-sectional view of an organic photovoltaic device according to an 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 disposed between the anode 110 and the cathode 120, wherein the organic layer 105 includes a light emitting layer 130 and an electric hole. The transmission auxiliary layer 142 and the 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 may be, for example, metal nickel, platinum, vanadium, chromium, copper, zinc, gold, or an alloy 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- (exthenyl- 1,2-dioxy) thiophene) (poly (3,4- (ethylene-1,2-dioxy) thiophene), PEDT), polypyrrole and polyaniline, but it is not limited to this.

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

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

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

The first compound having relatively strong electronic characteristics may 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, Substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C2 to C30 heterocyclyl, or a combination thereof, L ¹ to L ^{3 are} independently a single bond, substituted or unsubstituted C6 to C30 aryl, divalent substituted or unsubstituted C2 to C30 heterocyclyl, 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 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, and R ⁴ and R ^{5 are} independently present or fused to each other to form a ring.

The first compound includes a dibenzofuran or dibenzothiophene moiety and a nitrogen-containing six-membered ring moiety, and thus can increase the planarity of the molecular structure and at the same time effectively expand the LUMO energy band. Therefore, the first compound may have a structure that easily accepts electrons when an electric field is applied to an organic photovoltaic device manufactured by using the first compound, and thus a driving voltage of the organic photovoltaic device may be reduced. In addition, as the LUMO energy band is expanded, electronic stability is also increased, and thus the life of the organic optoelectronic device can be improved.

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

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

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

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

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

For example, Ar ¹ and Ar ² may be 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 triphenylene, substituted or unsubstituted pyridine , Substituted or unsubstituted pyrimidinyl, substituted or unsubstituted triazinyl, substituted or unsubstituted dibenzothienyl, substituted or unsubstituted dibenzofuranyl, Substituted or unsubstituted carbazolyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted quinolinyl, substituted or unsubstituted isoquinolinyl, substituted or unsubstituted Quinazoline, substituted or unsubstituted quinoxaline, or a combination thereof.

For example, Ar ¹ and Ar ² may be 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 fluorenyl.

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

[Group 1]

For example, L ¹ to L ³ may be independently a single bond, substituted or unsubstituted phenylene, substituted or unsubstituted phenylene, substituted or unsubstituted terphenylene , Substituted or unsubstituted naphthyl, substituted or unsubstituted anthryl, substituted or unsubstituted phenanthryl, substituted or unsubstituted dibenzothienyl, substituted or Unsubstituted dibenzofuranyl, substituted or unsubstituted carbazolyl, or substituted or unsubstituted fluorenyl. For example, L ¹ may be a single bond, substituted or unsubstituted metaphenylene, substituted or unsubstituted paraphenylene, substituted or unsubstituted metaphenylene, substituted Or unsubstituted para-phenylene or substituted or unsubstituted naphthyl. Here, "substituted" means that at least one hydrogen is replaced with 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 and deuterium, and when L ² is a single bond, Ar ² is not hydrogen and deuterium.

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

[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, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, Substituted or unsubstituted C3 to C30 heterocyclyl, substituted or unsubstituted silane, substituted or unsubstituted amine, halogen, cyano, or a combination thereof, R ^p and R ^{q are} independently present or Each other is fused 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 of 0 to 2.

For example, R ^p , R ^q , R ^r and R ^s can be independently hydrogen, deuterium, substituted or unsubstituted C1 to C4 alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted Substituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted terphenyl, substituted or unsubstituted fluorenyl, cyano, 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 property. ), And thus further improve the efficiency and life characteristics of organic optoelectronic devices.

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 inhibits 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 Formulas 1A-1 to 1A-3, but is not limited thereto.

[Chemical Formula 1A-1] [Chemical Formula 1A-2]

[Chemical Formula 1A-3]

In Chemical Formulas 1A-1 to 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 Formulas 1A-1 to 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 heterocyclyl, substituted or Unsubstituted silyl, substituted or unsubstituted amine, halogen, cyano, or a combination thereof, R ⁶ and R ⁷ exist independently or are fused to each other to form a ring, and R ⁹ to R ¹³ exist independently Alternatively, adjacent two 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 may be nitrogen, and Z ⁵ may be CR ^a .

For example, Z ⁵ and Z ⁶ may be nitrogen, and Z ⁴ may 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 Naphthyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothienyl, or substituted or unsubstituted fluorenyl.

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

The first compound may be, for example, one of the compounds of Group 2, but is not limited thereto.

[Group 2]

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

[Chemical Formula 2] [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 aryl group, and A ¹ and A ^{2 are} independently a 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 CR ^b and CR ^c , respectively, 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 heterocyclyl, or a combination thereof, R ²⁰ and R ^{21 are} independently present or fused to each other to form a ring, and R ²² and R ^{23 are} independently existed or fused to 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 the balance between the electrons and holes in the light emitting layer 130 can be increased, and an organic optoelectronic device having a long lifetime can be achieved.

For example, Y ¹ and Y ² may be independently a single bond, substituted or unsubstituted phenylene, substituted or unsubstituted phenylene, or substituted or unsubstituted terphenyl , Substituted or unsubstituted naphthyl, substituted or unsubstituted anthryl, substituted or unsubstituted phenanthryl, or substituted or unsubstituted fluorenyl.

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

For example, Y ¹ and Y ² may be independently a single bond, substituted or unsubstituted metaphenylene, substituted or unsubstituted paraphenylene, substituted or unsubstituted metaphenylene. Phenyl, substituted or unsubstituted p-biphenylyl, or substituted or unsubstituted p-naphthyl. Wherein "substituted" means that at least one hydrogen is replaced with deuterium, C1 to C20 alkyl, C6 to C12 aryl or cyano.

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 anthryl, substituted or unsubstituted phenanthryl, substituted or unsubstituted terphenylene, substituted or unsubstituted fluorenyl, 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 a bonding position between Chemical Formula 2 and Chemical Formula 3.

[Chemical Formula 2-A] [Chemical Formula 2-B] [Chemical Formula 2-C]

[Chemical Formula 2-D] [Chemical Formula 2-E]

In Chemical Formulas 2-A to 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 thereto.

[Group 3]

In one 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, it may include a weight ratio of about 1:99 to 99: 1, such as about 10:90 to 90:10, about 20:80 to 80:20, and about 30:70 to 70:30. The first compound and the second compound at about 40:60 to 60:40 or about 50:50.

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 small amounts to cause light emission, 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 A material that is excited multiple times to the triplet state or more and emits light (such as a metal complex). 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 an organometallic compound 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 Chemical Formula Z, but is not limited thereto.

[Chemical Formula Z] L ₂ MX

In Chemical Formula Z, M is a metal, and L and X are the same or different, and are ligands that form a complex compound 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 and X may be, for example, a bidentate ligand ( bidendate ligand).

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

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

[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 heterocyclyl , Substituted or unsubstituted silane groups, substituted or unsubstituted amine groups, halogens, cyano groups, or combinations thereof, R ⁵⁰ and R ⁵¹ independently exist or are fused with each other to form a ring, R ⁵² and R ⁵³ Existing independently or fused to each other to form a ring, and R ⁵⁴ and R ⁵⁵ independently present or fused to each other to form a ring.

The third compound has a high HOMO energy level and thus has sufficient hole injection characteristics. Therefore, the third compound is applied to the hole-transport auxiliary layer 142, and thus the hole mobility at the interface between the light-emitting layer 130 and the hole-transport layer 141 can be effectively improved, and the driving of the organic photoelectric device can be effectively reduced Voltage.

For example, L ⁴ to L ⁹ may be independently a single bond, substituted or unsubstituted phenylene, substituted or unsubstituted phenylene, substituted or unsubstituted terphenyl , Substituted or unsubstituted naphthyl, substituted or unsubstituted anthryl, substituted or unsubstituted phenanthryl, substituted or unsubstituted dibenzothienyl, substituted or Unsubstituted dibenzofuranyl, substituted or unsubstituted carbazolyl, or substituted or unsubstituted fluorenyl. For example, L ⁴ to L ⁹ may be independently a single bond, substituted or unsubstituted metaphenylene, substituted or unsubstituted paraphenylene, substituted or unsubstituted metaphenylene. Phenyl, substituted or unsubstituted p-biphenylyl, or substituted or unsubstituted p-naphthyl. Here, "substituted" means that at least one hydrogen is replaced with deuterium, C1 to C20 alkyl, C6 to C12 aryl or cyano.

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

For example, R ⁵⁰ to R ⁵⁵ may be 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 fluorenyl.

For example, R ⁵⁰ to R ⁵⁵ may be independently substituted or unsubstituted C6 to C30 aryl groups, or may be independently substituted or unsubstituted phenyl, substituted or unsubstituted Phenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthryl, substituted or unsubstituted phenanthryl, substituted or unsubstituted Ditriphenylene 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.

[Chemical Formula A]

In Chemical Formula A, X ³ is O or S, and 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 silane group, a substituted or unsubstituted amine group, a halogen, a cyano group, or a combination thereof, or L ⁴ to A group in 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 remainder of R ⁵⁰ to R ⁵⁵ may be independently a substituted or unsubstituted C6 to C30 aryl group.

For example, two 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 be independently a substituted or unsubstituted C6 to C30 aryl group.

For example, three of R ⁵⁰ to R ⁵⁵ may be a group represented by Chemical Formula A, and the remainder of R ⁵⁰ to R ⁵⁵ may be independently 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 thereto.

[Group 4]

The hole-transporting layer 141 is disposed between the anode 110 and the light-emitting layer 130, and can help the 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 level between a work function of a conductor forming the anode 110 and a HOMO level of a 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 is not limited thereto.

[Chemical Formula 5]

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 heterocyclyl or a combination thereof, R ¹¹⁸ and R ¹¹⁹ independently exist or fused with each other to form a ring, R ¹²⁰ and R ¹²¹ independently exist or fused with each other to form a ring, and Ar ¹⁰ to Ar ^{12 are} independently Substituted or unsubstituted C6 to C30 aryl or substituted or unsubstituted C2 to C30 heterocyclyl, and L ¹⁰ to L ^{13 are} independently a single bond, substituted or unsubstituted C6 to C30 Aryl, divalent substituted or unsubstituted C2 to C30 heterocyclyl, 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 be independently substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted Bisfluorenyl, substituted or unsubstituted terphenylene, substituted or unsubstituted anthryl, substituted or unsubstituted terphenyl, 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 thereto.

[Group 5]

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).

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. A dry film formation method such as plating) or a solution process forms an organic layer, and a cathode or an anode is formed on the organic layer.

The organic photoelectric device can be applied to a display device. 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

[Reaction Scheme 1]

a) Synthesis of intermediate B-24-1

15 grams (81.34 mmol) of cyanuric chloride was dissolved in 200 ml of anhydrous tetrahydrofuran in a 500 ml round-bottomed flask, and 1 equivalent of this was added dropwise thereto at 0 ° C under a nitrogen atmosphere. 4-Biphenylmagnesium bromide solution (0.5 M 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 mmol) 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 2 equivalents of dibenzofuran-3-boronic acid ( Chemical Abstracts Service (cas): 395087-89-5), 0.03 equivalent of tetrakistriphenylphosphine palladium and 2 equivalents of potassium carbonate, and the mixture was heated in a nitrogen atmosphere and Reflux. 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 compound B-24-2.

c) Synthesis of compound B-24

According to the same method as b), compound B-24 was synthesized using the intermediate B-24-2 and 1.1 equivalents of B- [1,1 ': 4', 1 ''-terphenyl] -3-ylboronic acid. Liquid chromatography (LC) / mass spectrum (MS) calculation: C45H29N3O 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 mmol) 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 An equivalent of tetra-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. (76% yield)

b) Synthesis of intermediate B-71-2

Put 24.53 g (88.02 mmol) of intermediate B-71-1 and 250 ml of dimethylformamide (DMF) into a 500 ml round bottom flask, and add 0.05 equivalent of dichlorodiphenyl to it. Dichlorodiphenylphosphinoferrocene palladium, 1.2 equivalents of 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, filtered through a 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. (70% yield)

c) Synthesis of compound B-71

According to the same method as in Synthesis Example a), by using the intermediates B-71-2 and 2,4-bis ([1,1'-biphenyl] -4-yl)- 6-Chloro-1,3,5-triazine synthesizes compound B-71. LC / MS calculation: C45H29N3O accurate mass: 627.2311 experimental value 628.25 [M + H]

Synthesis Example 3: Synthesis of Compound B-20

[Reaction Scheme 3]

a) Synthesis of intermediate B-20-1

Put 22.6 g (100 mmol) of 2,4-dichloro-6-phenyltriazine together with 100 ml of tetrahydrofuran, 100 ml of toluene and 100 ml of distilled water into a 500 ml round bottom flask, and add 0.9 equivalents of Dibenzofuran-3-boronic acid (CAS number: 395087-89-5), 0.03 equivalent of tetra-triphenylphosphine palladium, and 2 equivalent 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 in b) of Synthesis Example 3, using intermediate B-20-1 and 1.1 equivalents of (5'-phenyl [1,1 ': 3', 1 ''-terphenyl] -4-yl ) -Boric acid (CAS No. 491612-72-7) synthesizes compound B-20. LC / MS calculation: C45H29N3O accurate mass: 627.2311 experimental value 628.24 [M + H]

Synthesis Example 4: Synthesis of Compound B-124

[Reaction Scheme 4]

a) Synthesis of intermediate B-124-1

According to b) of Synthesis Example 1, the 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 without recrystallization using hexane via a flash column.

b) Synthesis of intermediate B-124-2

30 grams (88.02 mmol) of intermediate B-124-1 was added to 250 ml of dimethylformamide in a 500 ml round bottom flask, and 0.05 equivalent of dichlorodiphenylphosphine dicene was added thereto. Iron palladium), 1.2 equivalents of dipinacolate 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 a 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 in b) of Synthesis Example 3, Compound B-124 was synthesized using Intermediate B-124-2 and Intermediate B-17-1 in amounts of 1.0 equivalent, respectively. LC / MS calculation: C45H29N3O accurate mass: 627.2311 experimental value 628.22 [M + H]

Synthesis Example 5: Synthesis of Compound B-3

[Reaction Scheme 5]

a) Synthesis of intermediate B-3-1

Stir magnesium (7.86 g, 323 mmol) and iodine (1.64 g, 6.46 mmol) with 0.1 liters of tetrahydrofuran (THF) for 30 minutes under nitrogen, and slowly in it at 0 ° C for more than 30 minutes 1-Bromo-3,5-diphenylbenzene (100 g, 323 mmol) dissolved in 0.3 liter of tetrahydrofuran was added dropwise. The obtained mixed solution was slowly added dropwise to 64.5 g (350 mmol) of a 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), and after removing water therefrom with anhydrous MgSO _4, it was filtered 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 calculation: C45H27N3O2 accurate mass: 641.2103 experimental value 642.21 [M + H]

Synthesis Example 6: Synthesis of Compound HC-28

[Reaction Scheme 6]

a) Synthesis of intermediate HC-28-1

Add Intermediate A (30 g, 121.9 mmol), 1 equivalent of 4,4,4 ', 4', 5,5,5 ', 5'-octamethyl-2,2'-di (1, 3,2-dioxolane) (4,4,4 ', 4', 5,5,5 ', 5'-octamethyl-2,2'-bi (1,3,2-dioxaborolane) ), 2 equivalents of potassium acetate, 0.03 equivalents of 1,1'-bis (diphenylphosphino) ferrocene-palladium (II) chloride and 0.2 equivalents of tricyclohexylphosphine were added to a 500 ml flask In 300 ml of N, N-dimethylformamide, and the mixture was stirred at 130 ° C for 12 hours. When the reaction is completed, the reaction solution is extracted with water and EA to obtain an organic layer, and the organic layer is concentrated after removing water therefrom with magnesium sulfate, 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

29.66 grams (0.4 mole) of intermediate HC-28-1, 2 equivalents of intermediate B (1-bromo-20nitrobenzene), 2 equivalents of potassium carbonate, and 0.02 equivalents of tetrakis (triphenylphosphine) palladium (0) 200 ml of 1,4-dioxane and 100 ml of water were added to a 500 ml flask, and the mixture was heated at 90 ° C. under a stream of nitrogen for 16 hours. After removing the reaction solvent therefrom, dissolving the product obtained therefrom in dichloromethane, filtering through silica gel / diatomaceous earth, and recrystallizing with methanol after removing an appropriate amount of organic solvent therefrom, HC-28-2 (16.92 g, 58% yield) was obtained as a solid intermediate.

c) Synthesis of intermediate HC-28-3

8.7 g (30.2 mmol) of intermediate HC-28-2, 7.5 g (36.2 mmol) of intermediate C (2-bromonaphthalene), 4.3 g (45.3 mmol) of sodium tert-butoxide (NaOtBu ), 1.0 g (1.8 mmol) of Pd (dba) ₂ and 2.2 g of tri-tert-butylphosphine (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 removing xylene, 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 / diatomaceous earth, and After removing an appropriate amount of an organic solvent, it was recrystallized with acetone to obtain an intermediate HC-28-3 (9.83 g, 77% yield).

d) Synthesis of intermediate HC-28-4

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

e) Synthesis of compound HC-28

[Reaction Scheme 7]

Compound HC-28 was synthesized by the same method as in Synthesis Example c) using intermediate HC-28-4 and 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 in c) of Synthesis Example 9, using 4-bromobiphenyl as an intermediate instead of 2-bromonaphthalene, an intermediate HC-18-1 was synthesized.

b) Synthesis of intermediate HC-18-2

The intermediate HC-18-2 was synthesized by the same method as in d) of Synthesis Example 9.

c) Synthesis of intermediate HC-18-3

[Reaction Scheme 9]

According to the same method as in b) of Synthesis Example 1, intermediate HC-18-3 was synthesized using intermediate HC-18-A and intermediate HC-18-B.

d) Synthesis of compound HC-18

[Reaction Scheme 10]

Compound HC-18 was synthesized by the same method as in e) of Synthesis Example 9 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

[Reaction Scheme 11]

Intermediate HC-20-1 was synthesized using the intermediate HC-20-A and intermediate HC-20-B by the same method as in b) of Synthesis Example 1.

b) Synthesis of compound HC-20

[反应 计划 12]

Compound HC-20 was synthesized by the same method as in e) of Synthesis Example 9 using intermediate HC-18-2 and intermediate HC-20-1.

Synthesis Example 9: Synthesis of Compound HC-37

[Reaction Scheme 13]

Compound HC-37 was synthesized by the same method as in e) of Synthesis Example 9 using intermediate HC-28-4 and intermediate HC-18-3.

Synthesis Example 10: Synthesis of Compound C-14

[Reaction Scheme 14]

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

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

Manufacture of organic light-emitting diodes

Example 1

The glass substrate coated with a thin film of 1500 angstroms (Å) with indium tin oxide (ITO) was washed with distilled water. After washing with distilled water, the glass substrate is ultrasonically wave-washed with a solvent such as isopropyl alcohol, acetone, and methanol and dried, and then moved to a plasma cleaner and an oxygen plasma is used. Clean for 10 minutes and move to a 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 50 Angstroms thick, and C was 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 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 a dopant, A 400 Angstrom thick light emitting layer was formed on the hole transport auxiliary layer. Here, Compound B-24 and Compound HC-28 were used in a weight ratio of 3: 7. Subsequently, compounds D and Liq were simultaneously vacuum-deposited on the light-emitting layer at a ratio of 1: 1 to form a 300 angstrom thick electron transport layer, and Liq was vacuum-deposited to 15 angstroms thick and Al was vacuum deposited to a thickness of 1200 Angstroms to form a cathode, thereby fabricating 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-hexaazatriad Phenyl 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-fluoren-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 (naphthalene-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)

Examples 2 to 9 and Comparative Examples 1 to 6

Except that each compound shown in Table 1 was used in place 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 in place of compound F-148 for the hole transporting auxiliary layer, according to Example 1 An organic light emitting diode was manufactured in the same method.

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) Measurement of current density changes depending on voltage changes

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

(3) Measurement of brightness changes depending on voltage changes

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

(4) Measuring power efficiency

Use the brightness, current density, and voltage measured in (2) and (3) to calculate the power efficiency (lm / w).

[Table 1]

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

Although the invention has been described in connection with exemplary embodiments that are presently considered practical, it should be understood that the invention is not limited to the disclosed embodiments, but instead is intended to cover the spirit and scope included within the scope of the accompanying patent Various retouching and equivalent configurations.

300‧‧‧Organic Light Emitting Diode

110‧‧‧Anode

120‧‧‧ cathode

130‧‧‧Light-emitting layer

141‧‧‧hole transmission layer

142‧‧‧Electric hole transmission auxiliary layer

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

Claims (15)

An organic photovoltaic device includes: an anode and a cathode facing each other, a light emitting layer disposed between the anode and the cathode, a hole transmission layer disposed between the anode and the light emitting layer, and an electric hole A transmission auxiliary layer is disposed between the light emitting layer and the hole transmission layer. 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: [Chemical Formula 1 ] Among them, 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, Substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C2 to C30 heterocyclyl, or a combination thereof, L ¹ to L ^{3 are} independently a single bond, substituted or unsubstituted C6 to C30 aryl, divalent substituted or unsubstituted C2 to C30 heterocyclyl, 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 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, and R ⁴ and R ^{5 are} independently present or fused to each other to form a ring, [Chemical Formula 2] [Chemical Formula 3] Among them, 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 * in Chemical Formula 2 are bonded to two * in Chemical Formula 3, and the remaining two * in Chemical 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 heterocyclyl, or a combination thereof , R ²⁰ and R ²¹ independently exist or are fused with each other to form a ring, and R ²² and R ²³ independently exist or are fused with each other to form a ring, [Chemical Formula 4] Among them, in Chemical Formula 4, L ⁴ to L ^{9 are} independently a single bond, a substituted or unsubstituted C6 to C30 aryl 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 A cyclic group, a substituted or unsubstituted silane group, a substituted or unsubstituted amine group, a halogen, a cyano group, or a combination thereof, R ⁵⁰ and R ⁵¹ independently exist or are fused with each other to form a ring, R ⁵² and R ^{53 is} independently present or fused to each other to form a ring, and R ⁵⁴ and R ^{55 are} independently existed or fused to each other to form a ring. The organic photovoltaic device according to item 1 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 Triphenylene, 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 fluorenyl, substituted or unsubstituted quinolinyl, substituted or unsubstituted Isoquinolinyl, substituted or unsubstituted quinazoline, substituted or unsubstituted quinoxaline, or a combination thereof. The organic photovoltaic device according to item 1 of the scope of 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: [Group 1] . The organic photovoltaic device according to item 1 of the scope of patent application, wherein the first compound is represented by Chemical Formula 1A: [Chemical Formula 1A] Among them, in 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 heterocyclyl, or a combination thereof, L ² and L ^{3 are} independently a single bond, substituted or unsubstituted C6 to C30 aryl, divalent substituted or unsubstituted C2 to C30 heterocyclyl, 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 heterocyclyl, substituted or unsubstituted Silyl, substituted or unsubstituted amine, halogen, cyano, 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 to each other to form a ring, R ^p and R ^q independently exist or fused to each other to form a ring, R ^r and R ^s independently exist or fused to each other to form a ring, and n1 is 0 to An integer of 2. The organic photovoltaic 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: [Chemical Formula 1A-1] [Chemical Formula 1A-2] [Chemical Formula 1A-3] Among them, in Chemical Formulas 1A-1 to 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, and Ar ¹ and Ar ^{2 are} independently hydrogen, deuterium, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C2 to C30 Heterocyclyl or a combination thereof, L ² and L ^{3 are} independently a single bond, substituted or unsubstituted C6 to C30 aryl, divalent substituted or unsubstituted C2 to C30 heterocyclyl, 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 heterocyclyl, substituted or unsubstituted silyl, substituted or unsubstituted amine, halogen, cyano, or a combination thereof, R ¹ to R ³ exists independently or adjacent two of R ¹ to R ³ are combined to form a ring, R ⁴ and R ⁵ independently exist or are fused to each other to form a ring, R ⁶ and R ^{7 are} independently existed or fused to each other to form a ring, R ⁹ to R ¹³ independently present or ¹³ two adjacent R ⁹ to R are combined to form a ring, R ^P and R ^Q is independently present or fused with each other to form a ring, R ^S and R ^{R & lt} independently of the presence or fused with each other to form a ring, and n1 is an integer from 0 to 2. The organic photovoltaic 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 fluorenyl, 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 Phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted terphenyl, substituted or unsubstituted fluorenyl, cyano, or a combination thereof. The organic photovoltaic 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: [Chemical Formula 2-A] [Chemical Formula 2-B] [ Chemical formula 2-C] [Chemical Formula 2-D] [Chemical Formula 2-E] Among them, in Chemical Formulas 2-A to 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, 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, substituted or unsubstituted C3 to C30 heterocyclyl, or a combination thereof, R ²⁰ and R ^{21 are} independently present or fused to each other to form a ring, and R ²² and R ^{23 are} independently existed or fused to each other To form a ring. The organic photovoltaic device according to item 1 of the scope of patent application, wherein Y ¹ and Y ^{2 are} independently a single bond, substituted or unsubstituted phenylene, substituted or unsubstituted phenylene, or Substituted or unsubstituted naphthyl, 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 anthryl, substituted or unsubstituted phenanthryl, substituted or unsubstituted triphenylene, substituted or unsubstituted Hydrazone or a combination thereof. The organic photovoltaic device according to item 1 of the scope of patent application, wherein R ⁵⁰ to R ^{55 of} 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 fluorene Base or a combination thereof. The organic photovoltaic device according to item 1 of the scope of patent application, wherein R ⁵⁰ to R ^{55 of} Chemical Formula 4 are independently a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or Unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthryl, substituted or unsubstituted phenanthryl, substituted or unsubstituted terphenylene Or a combination. The organic photovoltaic device according to item 1 of the scope of 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] Among them, in Chemical Formula A, X ³ is O or S, and R ⁶⁰ to R ^{67 are} independently hydrogen, deuterium, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C6 to C30 aromatic Group, substituted or unsubstituted C3 to C30 heterocyclic group, substituted or unsubstituted silane group, substituted or unsubstituted amine group, halogen, cyano group or combination thereof, or L of Chemical Formula 4 A group in 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 optoelectronic device according to item 1 of the scope of patent application, wherein the hole transport auxiliary layer contacts the light emitting layer. The organic photovoltaic device according to item 1 of the scope of patent application, wherein the hole transport layer contains a compound represented by Chemical Formula 5: [Chemical Formula 5] Among them, 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 Substituted C2 to C30 heterocyclic groups or combinations thereof, R ¹¹⁸ and R ¹¹⁹ independently exist or are fused with each other to form a ring, R ¹²⁰ and R ^{121 are} independently existed or fused with each other to form a ring, and Ar ¹⁰ to Ar ^{12 are} independent 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, substituted or unsubstituted C6 to C30 aryl, divalent substituted or unsubstituted C2 to C30 heterocyclyl, or a combination thereof. The organic photovoltaic 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 fluorenyl, substituted or unsubstituted difluorenyl, substituted or unsubstituted Substituted terphenylene, substituted or unsubstituted anthryl, substituted or unsubstituted terphenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted Dibenzothienyl or a combination thereof. A display device includes the organic photovoltaic device according to any one of items 1 to 14 of the scope of patent application.