KR102361170B1 - A orthoterphenyl compound including pyridine, and organic light emitting diode having the same - Google Patents

Abstract

The present invention relates to a compound for an organic light emitting diode, an organic light emitting diode using the same, and an electronic device including the organic light emitting diode. , long lifespan and high color purity can be achieved.

Description

A compound of an orthoterphenyl structure including pyridine and an organic light emitting diode containing the same

The present invention relates to a compound for an organic light emitting diode, an organic electric device using the same, and an electronic device thereof.

In general, the organic light emitting phenomenon refers to a phenomenon in which electric energy is converted into light energy using an organic material. An organic light emitting diode using an organic light emitting phenomenon usually has a structure including an anode and a cathode and an organic layer therebetween. Here, the organic layer is often formed of a multilayer structure composed of different materials in order to increase the efficiency and stability of the organic light emitting diode, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, etc. can be made with

A material used as an organic layer in an organic light emitting diode may be classified into a light emitting material and a charge transport material, for example, a hole injection material, a hole transport material, an electron transport material, an electron injection material, etc. according to their function. In addition, the light emitting material can be classified into a high molecular type and a low molecular type according to the molecular weight, and can be classified into a fluorescent material derived from a singlet excited state of an electron and a phosphorescent material derived from a triplet excited state of an electron according to the light emission mechanism. have. In addition, the light emitting material may be divided into blue, green, and red light emitting materials and yellow and orange light emitting materials necessary for realizing a better natural color according to the emission color.

2. Description of the Related Art An organic light emitting diode (OLED) is a self-luminous device and is used in a display or lighting. Recently, organic light emitting diodes are being applied to display panels, and compared to conventional liquid crystal displays, the viewing angle is wide and the contrast is excellent, the response time is fast, the luminance, driving voltage and response speed characteristics are excellent, and the advantages of multicolor are possible. Have.

These organic light emitting diodes are driven by direct current, and when a direct current voltage is applied between the anode and the cathode, holes injected from the anode move to the emission layer via the hole injection/transport layer, and electrons injected from the cathode pass through the electron injection/transport layer move to the light emitting layer. Holes and electrons reaching the emission layer generate excitons in an excited state through recombination, and the excitons change to a ground state and emit light of a specific wavelength.

When excitons are formed, 25% of singlet states and 75% of triplet states are formed according to the quantum spin statistical law. Light-emitting materials can be largely divided into fluorescent materials and phosphorescent materials. In the case of fluorescent materials, since they emit light using only a singlet state, theoretically, quantum efficiency is very low. Therefore, in order to improve the efficiency of the light emitting layer or the efficiency of the organic light emitting diode, triplet excitons should be utilized as much as possible.

Accordingly, in the case of a phosphorescent material containing a heavy metal such as iridium (Ir) or platinum (Pt), triplet excitons can be converted into light, and thus a highly efficient organic light emitting diode device can be manufactured. However, the cost of iridium (Ir) or platinum (Pt) is expensive and the supply of materials is limited, and especially in the case of blue phosphorescent materials, the problem of device lifetime must be solved.

Efficiency, lifespan, and driving voltage are related to each other, and when the efficiency is increased, the driving voltage is relatively decreased. It shows a tendency to increase the lifespan.

Therefore, it is necessary to develop a light-emitting material that has high thermal stability and can efficiently achieve charge balance in the light-emitting layer.

Accordingly, as a result of research to provide a light emitting material of a new design, the present inventors have derived the present invention through a compound having an orthoterphenyl structure including pyridine in its backbone structure.

An object of the present invention is to provide an organic material having improved efficiency and improved lifespan, and an organic light emitting diode containing the same. In addition, it is intended to improve the color purity and lifespan characteristics of blue, green, and red light emitting materials applicable to displays.

In one aspect, the present invention is substituted or unsubstituted by one or more substituents (R); It is a compound of the orthoterphenyl structure composed of one or two pyridines and benzene.

In another aspect, the present invention provides an organic light emitting diode using the compound and an electronic device thereof.

By using the compound according to the present invention, there is an effect of achieving a high glass transition temperature, high molecular stability, high luminous efficiency, long lifespan, and high color purity.

1 is a cross-sectional view showing an organic light emitting diode according to an embodiment of the present invention.
2 to 8 are compounds used in the organic light emitting diode of the present invention.

Hereinafter, preferred embodiments of the present invention will be described with reference to the accompanying drawings.

In order to describe the present embodiments, it should be noted that, in adding reference numerals to components of each drawing, the same components are given the same reference numerals as much as possible even though they are indicated in different drawings. In addition, in describing the present invention, if it is determined that a detailed description of a related known configuration or function may obscure the gist of the present invention, the detailed description thereof will be omitted. In the drawings referenced below, no scale ratio applies.

In describing the components of the present invention, terms such as first, second, A, B, (a), (b), etc. may be used. These terms are only for distinguishing the elements from other elements, and the essence, order, or order of the elements are not limited by the terms.

When it is described that a component is “connected”, “coupled” or “connected” to another component, the component may be directly connected or connected to the other component, but another component is between each component. It should be understood that elements may also be “connected,” “coupled,” or “connected.”

Further, when a component, such as a layer, membrane, region, plate, etc., is said to be “on” or “on” another component, this means not only when it is “directly above” another component, but also when another component is in between. It should be understood that cases may be included. Conversely, when it is said that an element is "on top of" another part, it should be understood to mean that there is no other part in the middle.

Terms used in this specification and the appended claims are as follows, unless otherwise stated, without departing from the spirit of the present invention.

As used herein, the term "halo" or "halogen" includes fluorine (F), chlorine (Cl), bromine (Br), and iodine (I), unless otherwise specified.

The term "alkyl" or "alkyl group" as used in this application, unless otherwise specified, has 1 to 60 carbons linked by a single bond, straight chain alkyl group, branched chain alkyl group, cycloalkyl (alicyclic) group, alkyl-substituted means a radical of saturated aliphatic functional groups including cycloalkyl groups and cycloalkyl-substituted alkyl groups. In addition, it may be used including “alkenyl” or “alkynyl” below.

The term "alkenyl" or "alkynyl" as used in this application has a double or triple bond instead of a single bond in the "alkyl", respectively, unless otherwise specified, and includes a straight or branched chain group, 2 It has a carbon number of to 60, but is not limited thereto.

As used herein, the term "cycloalkyl" refers to an alkyl forming a ring having 3 to 60 carbon atoms, unless otherwise specified, and is not limited thereto.

The terms "aryl group" and "arylene group" used in the present application have 6 to 60 carbon atoms, respectively, unless otherwise specified, but are not limited thereto. In the present application, the aryl group or the arylene group includes a single ring type, a ring aggregate, a fused multiple ring-based compound, and the like. For example, the aryl group may include a phenyl group, a monovalent functional group of biphenyl, a monovalent functional group of naphthalene, a fluorenyl group, and a substituted fluorenyl group, and the arylene group may include a fluorenylene group, a substituted fluorenylene group. may include a group.

Since the aryl group in the present application includes a ring aggregate, the aryl group includes biphenyl and terphenyl in which a single aromatic benzene ring is connected by a single bond.

As used herein, the term "fused multiple ring system" refers to a fused ring type that shares at least two atoms, and includes a fused ring system of two or more hydrocarbons and at least one heteroatom. and a form in which at least one heterocyclic system is fused. The fused multiple ring system may be an aromatic ring, a heteroaromatic ring, an aliphatic ring, or a combination of these rings.

The term "heterocyclic group" used in this application includes not only aromatic rings such as "heteroaryl group" or "heteroarylene group" but also non-aromatic rings, and unless otherwise specified, each carbon number including at least one heteroatom It means a ring of 2 to 60, but is not limited thereto. As used herein, the term "heteroatom" refers to N, O, S, P or Se, unless otherwise specified, and the heterocyclic group includes a monocyclic group, a ring aggregate, a fused multiple ring system, etc. including a heteroatom. it means.

Also, unless otherwise explicitly stated, in the term "substituted or unsubstituted" used in this application, "substitution" means hydrogen, deuterium, C ₁ -C ₉ alkyl group, C ₃ -C ₃₀ cycloalkyl group, C ₆ - C ₃₀ Aryl group, C ₈ -C ₃₀ Alkylaryl group, C ₈ -C ₃₀ Arylalkyl group, C ₂ -C ₃₀ Heteroaryl group, aryloxy group, arylamine, fused arylamine group, phosphine Or it means substituted with one or more substituents selected from the group consisting of a phosphine oxide group, a thiol group, a sulfoxide or a sulfone group, but is not limited to these substituents.

In the present application, the 'functional group name' corresponding to the aryl group, arylene group, heterocyclic group, etc. exemplified as examples of each symbol and its substituents may be described as 'the name of the functional group reflecting the valence', but it is described as 'the name of the parent compound' You may.

Hereinafter, a stacked structure of an organic light emitting diode including the compound of the present invention will be described with reference to FIG. 1 .

Referring to FIG. 1 , referring to FIG. 1 , an organic light emitting diode is disposed between an anode 10 and a cathode 70 , a light emitting layer 40 disposed between these two electrodes, and an anode 10 and a light emitting layer 40 . and a hole conductive layer 20 and an electron conductive layer 50 disposed between the light emitting layer 40 and the cathode 70 .

The hole conductive layer 20 may include a hole transport layer 25 for transporting holes and a hole injection layer 23 for facilitating injection of holes. In addition, the electron conductive layer 50 may include an electron transport layer 55 for transporting electrons and an electron injection layer 53 for facilitating electron injection.

In addition, a first exciton blocking layer (not shown) may be disposed between the emission layer 40 and the hole transport layer 25 . Also, a second exciton blocking layer (not shown) may be disposed between the emission layer 40 and the electron transport layer 55 . However, the present invention is not limited thereto, and the electron transport layer 55 may serve as the second exciton blocking layer, or the hole transport layer 25 may serve as the first electron blocking layer.

When a forward bias is applied to the organic light emitting diode, holes from the anode 10 flow into the emission layer 40 , and electrons from the cathode 70 flow into the emission layer 40 . Electrons and holes introduced into the emission layer 40 combine to form excitons, and light is emitted as the excitons transition to a ground state.

The light emitting layer 40 may be made of a single light emitting material, and may include a light emitting host material and a light emitting dopant material. When the light emitting layer 40 includes a light emitting host material and a light emitting dopant material, electrons and holes introduced into the light emitting layer 40 combine in the light emitting host material to form excitons, and then the excitons are transferred to the light emitting dopant material to form a base state can be transferred. The emission layer 40 including the emission host material and the emission dopant material may be a phosphorescent emission layer or a fluorescent emission layer, for example, a delayed fluorescent emission layer.

Any one of the compounds according to the present invention may be used for any one of the organic layers 20, 40, and 50 of the organic light emitting diode. Specifically, the compound may be used as any one of a hole injection material, a hole transport material, an exciton blocking material, a light emitting host material, a light emitting dopant material, an electron injection material, and an electron transport material.

In detail, the organic material may be used as a light emitting dopant material, and in this case, the light emitting layer 40 may be a delayed fluorescent light emitting layer.

In addition, the organic material may be used as a sensor for a general fluorescent dopant. In this case, the light emitting layer may be a light emitting layer composed of a delayed fluorescent host and a fluorescent dopant.

In addition, the host of the light emitting layer 40, in addition to the compound according to the present invention, mCP (N,N-dicarbazolyl-3,5-benzene), TSPO1 (diphenylphosphine oxide-4-(triphenylsilyl)phenyl), DPEPO (bis[2- (diphenylphosphino)phenyl]ether oxide), BSB (4,4 ′-bistriphenylsilanyl-biphenyl), UGH3 (m-bis- (triphenylsilyl)benzene), SimCP(3,5-di(N-carbazolyl)tetraphenylsilane), SimCP2 ( bis(3,5-di(9H-carbazol-9-yl)phenyl)diphenylsilane), CzSi(9-(4-tertbutylphenyl)-3,6-bis(triphenylsilyl)-9H-carbazole), SiCa(Diphenyldi(4 -(9-carbazoly)phenyl)silane), DCPPO((3,5-di(9H-carbazole-9-yl)phenyl)diphenylphosphine oxide), DFCz (2,8-di(9Hcarbazol-9-yl)dibenzo[ b,d]furan), DBT1(2,8-di(9H-carbazol-9-yl)dibenzo[b,d]thiophene), 26mCPy (2,6-bis(N-carbazolyl)pyridine), or any of these It may be a mixture of two or more.

In addition, the host is Alq3, CBP (4,4'-N,N'-dicarbazole-biphenyl), 9,10-di (naphthalen-2-yl) anthracene, TPBI (1,3,5-tris ( N-phenylbenzimidazol-2-yl)benzene (1,3,5-tris(N-phenylbenzimidazole-2-yl)benzene)), TBADN (3-tert-butyl-9,10-di(naphth- 2-day) anthracene).

The anode 10 may be a conductive metal oxide, metal, metal alloy, or carbon material. Conductive metal oxides include indium tin oxide (ITO), fluorine tin oxide (FTO), antimony tin oxide (ATO), fluorine doped tin oxide (FTO), SnO ₂ , ZnO, or a combination thereof. Suitable metals or metal alloys as anode 10 may be Au and CuI. The carbon material may be graphite, graphene, or carbon nanotubes.

The hole injection layer 23 and/or the hole transport layer 25 is a layer having a HOMO level between the work function level of the anode 10 and the HOMO level of the light emitting layer 40, from the anode 10 to the light emitting layer 40 It functions to increase the injection or transport efficiency of holes. In addition, the electron injection layer 53 and/or the electron transport layer 55 are layers having a LUMO level between the work function level of the cathode 70 and the LUMO level of the light emitting layer 40, and in the cathode 70, the light emitting layer 40 ) to increase the injection or transport efficiency of electrons.

The hole injection layer 23 or the hole transport layer 25 may include a material commonly used as a hole transport material, and one layer may include layers of different hole transport materials.

The hole transport material is, for example, mCP (N,N-dicarbazolyl-3,5-benzene); PEDOT:PSS (poly(3,4-ethylenedioxythiophene):polystyrenesulfonate); NPD (N,N′-di(1-naphthyl)-N,N′-diphenylbenzidine); N,N'-diphenyl-N,N'-di(3-methylphenyl)-4,4'-diaminobiphenyl (TPD); N,N'-diphenyl-N,N'-dinaphthyl-4,4'-diaminobiphenyl; N,N,N'N'-tetra-p-tolyl-4,4'-diaminobiphenyl; N,N,N'N'-tetraphenyl-4,4'-diaminobiphenyl; porphyrin compound derivatives such as copper(II)1,10,15,20-tetraphenyl-21H,23H-porphyrin; TAPC(1,1-Bis[4-[N,N'-Di(ptolyl)Amino]Phenyl]Cyclohexane); triarylamine derivatives such as N,N,N-tri(p-tolyl)amine, 4,4′,4′-tris[N-(3-methylphenyl)-N-phenylamino]triphenylamine; carbazole derivatives such as N-phenylcarbazole and polyvinylcarbazole; phthalocyanine derivatives such as metal-free phthalocyanine and copper phthalocyanine; starburst amine derivatives; enamine stilbene derivatives; derivatives of aromatic tertiary amines and styryl amine compounds; and polysilane. Such a hole transport material may serve as the first exciton blocking layer.

The second exciton blocking layer serves to prevent triplet excitons or holes from diffusing toward the cathode 70 , and may be arbitrarily selected from known hole blocking materials. For example, an oxadiazole derivative, a triazole derivative, a phenanthroline derivative, etc. can be used.

The electron transport layer 55 is, in addition to the compound according to the present invention, TSPO1 (diphenylphosphine oxide-4-(triphenylsilyl)phenyl), TPBi(1,3,5-tris(N-phenylbenzimidazol-2-yl)benzene), Tris (8-quinolinolate) aluminum (Alq3), 2,5-diaryl silol derivative (PyPySPyPy), perfluorinated compound (PF-6P), COTs (Octasubstituted cyclooctatetraene), Bphen (4,7-diphenyl) -1,10-phenanthroline (4,7-diphenyl-1,10-phenanthroline).

The electron injection layer 53 may be, for example, LiF, NaCl, CsF, Li2O, BaO, BaF2, or Liq (lithium quinolate). The cathode 70 is a conductive film having a lower work function than the anode 10, for example, aluminum, magnesium, calcium, sodium, potassium, indium, yttrium, lithium, silver, lead, metals such as cesium, or these It can be formed using a combination of two or more types of

The anode 10 and the cathode 70 may be formed using a sputtering method, a vapor deposition method, or an ion beam deposition method. The hole injection layer 23, the hole transport layer 25, the light emitting layer 40, the exciton blocking layer, the electron transport layer 55, and the electron injection layer 53 are independent of each other by a deposition method or a coating method, for example, spraying. , spin coating, dipping, printing, doctor blading, or electrophoresis. The scope of the present invention is not limited by this formation method.

The organic light emitting diode may be disposed on a substrate (not shown). The substrate may be disposed under the anode 10 or disposed above the cathode 70 . In other words, the anode 10 may be formed before the cathode 70 or the cathode 70 may be formed before the anode 10 on the substrate.

The substrate may be a light-transmitting substrate as a flat member, and in this case, the substrate may include glass; ceramic materials; It may be made of a polymer material such as polycarbonate (PC), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyimide (PI), polypropylene (PP), and the like. However, the present invention is not limited thereto, and the substrate may be a metal substrate capable of reflecting light.

The organic light emitting diode according to FIG. 1 may further include a protective layer (not shown) and an encapsulation layer (not shown). The protective layer may be disposed on the capping layer, and the encapsulation layer may be disposed on the capping layer, and may be formed to cover side portions of at least one of the anode, the cathode and the organic layer in order to protect the anode, the cathode and the organic layer.

The protective layer may provide a planarized surface so that the encapsulation layer is uniformly formed, and may serve to protect the first electrode, the second electrode, and the organic layer during the manufacturing process of the encapsulation layer.

The encapsulation layer may serve to prevent penetration of external oxygen and moisture into the organic light emitting diode.

The organic light emitting diode according to an embodiment of the present invention may be a top emission type, a back emission type, or a double side emission type depending on the material used.

Another embodiment of the present invention may include a display device including the organic light emitting diode of the present invention described above, and an electronic device including a controller for controlling the display device.

Hereinafter, the compound according to one aspect of the present invention will be described.

The compound according to one aspect of the present invention is unsubstituted or substituted by one or more substituents (R); A compound of orthoterphenyl structure comprising one or two pyridines and benzene,

The substituents (R) are each independently a substituted or unsubstituted C ₄ -C ₃₀ alkyl group; a substituted or unsubstituted C ₅ -C ₃₀ cycloalkyl group; a substituted or unsubstituted C ₅ to C ₃₀ aryl group; a substituted or unsubstituted C ₆ -C ₃₀ aralkyl group; A substituted or unsubstituted C ₃ -C ₃₀ heteroaryl group; a substituted or unsubstituted aryloxy group; substituted or unsubstituted arylamine; a substituted or unsubstituted fused arylamine group; a substituted or unsubstituted phosphine or phosphine oxide group; a substituted or unsubstituted thiol group; A substituted or unsubstituted sulfoxide or sulfone group; is a compound.

Preferably, the substituents (R) are each independently hydrogen, deuterium, C ₁ -C ₉ alkyl group, C ₃ -C ₃₀ cycloalkyl group, C ₆ -C ₃₀ aryl group, C ₈ -C ₃₀ alkyl Aryl group, C ₈ -C ₃₀ Arylalkyl group, C ₂ -C ₃₀ Heteroaryl group, aryloxy group, arylamine, fused arylamine group, phosphine or phosphine oxide group, thiol group, sulfoxide or sulfone It may be substituted with one or more substituents selected from the group consisting of groups.

In addition, it is preferable that the substituents (R) are bonded to each other to form a ring.

A ring formed by bonding the substituents (R) to each other is a C ₆ ~ C ₆₀ aromatic ring group; fluorenyl group; O, N, S, Si and P containing at least one heteroatom C ₂ ~ C ₆₀ A heterocyclic group; Or C ₃ ~ C ₆₀ It is preferably an aliphatic group.

Preferably, the compound may be one of the following Chemical Formulas 1 to 2, but is not limited thereto.

<Formula 1> <Formula 2>

In Formula 1 or 2, R is the same as the substituent (R).

Also preferably, the compound may be one of the following Chemical Formulas 3 to 9, but is not limited thereto.

<Formula 3> <Formula 4> <Formula 5>

<Formula 6> <Formula 7> <Formula 8>

<Formula 9>

In Formulas 3 to 9, R is the same as the substituent (R).

Meanwhile, the compound of Formulas 1 to 9 may be one of the following compounds P-1 to P-21, but is not limited thereto.

In another embodiment of the present invention, the present invention provides a first electrode; a second electrode; and an organic layer formed between the first electrode and the second electrode, wherein the organic layer includes the compound represented by Formula 1 alone or in combination.

The organic layer includes at least one of a hole injection layer, a hole transport layer, an exciton blocking layer, a light emitting layer, an electron transport auxiliary layer, an electron transport layer, and an electron injection layer. That is, at least one of a hole injection layer, a hole transport layer, an exciton blocking layer, a light emitting layer, an electron transport auxiliary layer, an electron transport layer, or an electron injection layer included in the organic layer may include a compound represented by Formula 1.

Preferably, the organic layer includes the light emitting layer or the electron transport layer. That is, the compound may be included in the light emitting layer or the electron transport layer.

The organic layer includes two or more stacks including a hole transport layer, a light emitting layer, and an electron transport layer sequentially formed on the anode.

Another aspect of the present invention is to provide an electronic device including a display device including an organic light emitting diode including the compound represented by Chemical Formula 1 and a controller for driving the display device.

In an embodiment of the present invention, the compound of Formula 1 may be included alone, the compound may be included in a combination of two or more different types, or the compound may be included in a combination of two or more other compounds.

Hereinafter, a synthesis example of a compound represented by Formula 1 and a manufacturing example of an organic light emitting diode according to the present invention will be described in detail with reference to Examples, but the present invention is not limited to the following examples.

<Synthesis example>

The final product according to the present invention may be synthesized as follows, but is not limited thereto.

<P- 1> of Synthesis example

Synthesis of <Intermediate-1>: 2,6-dibromopyridine (15.0 g, 63.32 mmol) and carbazole (8.8 g, 52.56 mmol) were placed in a 500 ml two-necked round-bottom flask, and 1,4-dioxane 400 ml After dissolving in CuI ₂ (0.60 g, 3.17 mmol) and tripotassium phosphate (13.1 g, 95.0 mmol) were added. Thereafter, 1,2-diaminocyclohexane (1.45 g, 12.6 mmol) was injected and the mixture was stirred under reflux for 24 hours. After completion of the reaction and cooling to room temperature, the reaction product was extracted with methylene chloride (MC) and distilled water, and the organic layer was dried with magnesium sulfate and the solvent was removed by distillation under reduced pressure. The reaction product was further purified by column chromatography using a methylene chloride/hexane mixed solvent, and after drying, 9-(6-bromopyridin-2-yl) -9H -carbazole (Intermediate 1) as a pure white solid was 10.5 g was obtained. [Yield: 51%, MS (FD+) m/z 323]

Synthesis of <Intermediate-2>: Intermediate 1 (5.0 g, 15.5 mmol) and bis(pinacolato)diboron (5.1 g, 20.1 mmol) were placed in a 250ml 2-neck round-bottom flask, and 1,4-dioxane 100 After dissolving in ml, potassium acetate (4.6 g, 46.4 mmol) and [1,1'-bis (diphenylphosphino) ferrocene] dichloropalladium (II) (0.6 g, 0.7 mmol) were added, followed by 24 hours while stirring under reflux. After completion of the reaction, after cooling to room temperature, the reactant was extracted with methylene chloride and distilled water, and the organic layer was dried with magnesium sulfate to remove moisture, and then the solvent was removed by distillation under reduced pressure. The reaction product was further purified by column chromatography using a methylene chloride/hexane mixed solvent, and after drying, 9-(6-(4,4,5,5-tetramethyl-1,3,2-diox) as a pure white solid 2.5 g of saborolan -2-yl)pyridin-2-yl)-9H-carbazole (Intermediate 2) was obtained. [Yield: 44%, MS (FD+) m/z 370]

Synthesis of <P-1>: After dissolving 1,2-dibromobenzene (2.3 g, 9.7 mmol) and Intermediate 2 (7.6 g, 20.5 mmol) in 90 ml of tetrahydrofuran in a 250 ml 2-neck round-bottom flask, 30ml of 2M potassium carbonate (4.7 g, 34.1 mmol) aqueous solution was added. After the addition of tetrakis(triphenylphosphine)palladium(0) (1.2 g, 1.0 mmol), the mixture was stirred under reflux for 24 hours. After completion of the reaction and cooling to room temperature, the reaction product was extracted with methylene chloride and distilled water, and the organic layer was dried with magnesium sulfate and then the solvent was removed by distillation under reduced pressure. The reaction product was further purified by column chromatography using a mixed solvent of methylene chloride/hexane, and 1,2-bis(6-( 9H -carbazol-9-yl)pyridin-2-yl) as a pure white solid after drying 2.0 g of benzene (P-1) was obtained. [Yield: 40%, MS (FD+) m/z 562]

<P- 3> of Synthesis example

Synthesis of <Intermediate-3>: 2,3-dibromopyridine (15.0 g, 63.32 mmol) and carbazole (8.8 g, 52.56 mmol) were placed in a 500 ml two-necked round-bottom flask, and 1,4-dioxane 400 ml After dissolving in CuI ₂ (0.60 g, 3.17 mmol) and tripotassium phosphate (13.1 g, 95.0 mmol) were added. Thereafter, 1,2-diaminocyclohexane (1.45 g, 12.6 mmol) was injected and the mixture was stirred under reflux for 24 hours. After completion of the reaction and cooling to room temperature, the reaction product was extracted with methylene chloride and distilled water, and the organic layer was dried with magnesium sulfate and then the solvent was removed by distillation under reduced pressure. The reaction product was further purified by column chromatography using a methylene chloride/hexane mixed solvent, and after drying, 9-(3-bromopyridin-2-yl) -9H -carbazole (Intermediate 1) as a pure white solid was obtained. 10.5 g were obtained. [Yield: 51%, MS (FD+) m/z 323]

Synthesis of <Intermediate-4>: Put Intermediate 1 (5.0 g, 15.5 mmol) and bis(pinacolato)diboron (5.1 g, 20.1 mmol) in a 250ml 2-neck round-bottom flask, and 1,4-dioxane 100 ml After dissolving in potassium acetate (4.6 g, 46.4 mmol) and [1,1'-bis (diphenylphosphino) ferrocene] dichloropalladium (II) (0.6 g, 0.7 mmol) was added and refluxed for 24 hours. Stir. After completion of the reaction, after cooling to room temperature, the reaction product was extracted with methylene chloride and distilled water, the organic layer was dried with magnesium sulfate to remove moisture, and then the solvent was removed by distillation under reduced pressure. The reaction product was further purified by column chromatography using a mixed solvent of methylene chloride/hexane, and after drying, 9-(3-(4,4,5,5-tetramethyl-1,3,2-diox) as a pure white solid 2.5 g of saborolan -2-yl)pyridin-2-yl)-9H-carbazole (Intermediate 4) was obtained. [Yield: 44%, MS (FD+) m/z 370]

Synthesis of <P-3>: After dissolving 1,2-dibromobenzene (2.3 g, 9.7 mmol) and Intermediate 4 (7.6 g, 20.5 mmol) in 90 ml of tetrahydrofuran in a 250 ml 2-neck round-bottom flask, 30ml of 2M potassium carbonate (4.7 g, 34.1 mmol) aqueous solution was added. After the addition of tetrakis(triphenylphosphine)palladium(0) (1.2 g, 1.0 mmol), the mixture was stirred under reflux for 24 hours. After completion of the reaction and cooling to room temperature, the reaction product was extracted with methylene chloride and distilled water, and the organic layer was dried with magnesium sulfate and then the solvent was removed by distillation under reduced pressure. The reaction product was further purified by column chromatography using a mixed solvent of methylene chloride/hexane, and 1,2-bis(2-( 9H -carbazol-9-yl)pyridin-3-yl as a pure white solid after drying. ), 2.0 g of benzene (P-3) was obtained. [Yield: 40%, MS (FD+) m/z 562]

<P- 8> of Synthesis example

Synthesis of <P-8>: 2,3-dibromopyridine (2.0 g, 8.4 mmol) and (3-( 9H -carbazol-9-yl)phenyl)boronic acid (5.1 g, 17.7 mmol) was put into a 250ml 2-neck round-bottom flask, dissolved in 100 ml of tetrahydrofuran, and then 30 ml of 2 M potassium carbonate (3.5 g, 25.3 mmol) was added. Thereafter, tetrakis(triphenylphosphine)palladium(0) (0.6 g, 0.9 mmol) was added, and the mixture was stirred under reflux for 24 hours. After cooling to room temperature, the reactant was extracted with methylene chloride and distilled water, and the organic layer was dried with magnesium sulfate and then the solvent was removed by distillation under reduced pressure. The reaction product was further purified by column chromatography using a methylene chloride/hexane mixed solvent, and after drying, a pure white solid 9,9'-(pyridine-2,3-diylbis(3,1-phenylene)) 1.9 g of bis(9 H -carbazole) (P-8) was obtained. [Yield: 40%, MS (FD+) m/z 487]

<P- 14> of Synthesis example

Synthesis of <P-14>: 2,3-dibromopyridine (2.0 g, 8.4 mmol) and (3-( 9H -carbazol-9-yl)phenyl)boronic acid (5.1 g, 17.7 mmol) was placed in a 250ml 2-neck round-bottom flask, dissolved in 100 ml of tetrahydrofuran, and 30 ml of 2 M potassium carbonate (3.5 g, 25.3 mmol) was added thereto. Thereafter, tetrakis(triphenylphosphine)palladium(0) (0.6 g, 0.9 mmol) was added, and the mixture was stirred under reflux for 24 hours. After cooling to room temperature, the reactant was extracted with methylene chloride and distilled water, the organic layer was dried with magnesium sulfate, and the solvent was removed by distillation under reduced pressure. The reaction product was further purified by column chromatography using a methylene chloride/hexane mixed solvent, and after drying, a pure white solid 9,9'-(pyridine-2,3-diylbis(3,1-phenylene)) 1.9 g of bis(9 H -carbazole) (P-14) were obtained. [Yield: 40%, MS (FD+) m/z 487]

organic light emitting diode Manufacturing evaluation

( Example One) delayed fluorescence organic light emitting diode Produce

(ITO/PEDOT:PSS/TAPC/mCP/P-1:DMAC-DPS/TSPO1/TPBi/LiF/Al)

The glass substrate on which the anode, ITO was deposited, was washed in ultrasonic waves for 30 minutes using tertiary distilled water and isopropyl alcohol. After surface treatment of the washed ITO substrate using short-wavelength ultraviolet light, poly(3,4-edylenedioxythiophene):poly(styrenesulfonate) (PEDOT: PSS, see FIG. 2) was applied to 60 nm A hole injection layer was formed by spin coating to a thickness.

Then, 1,1-bis[4-[ N , N' -di( p -tolyl)amino]phenyl]cyclohexane (TAPC ^, see FIG. ³ ) was added at a pressure of 1x10-6 torr at 0.1 nm/s It was deposited at a rate to form a hole transport layer of 20 nm.

Then, N , N -dicarbazolyl-3,5-benzene (mCP, see FIG. 4) was deposited at a rate of 0.1 nm/s at a pressure of 1x10 ^-6 torr to form an exciton-blocking layer of 10 nm.

Then, at a pressure of 1x10 ^-6 torr, the compound P-1 of the present invention as a host material at a rate of 0.1 nm/s, and DMAC-DPS (see FIG. 5) as a delayed fluorescence dopant material at a rate of 0.005 nm/s By vacuum deposition, a light emitting layer in which a dopant was doped 20% was formed on the host.

Diphenylphosphine oxide-4-(triphenylsilyl)phenyl (TSPO1, see FIG. 6) and 1,3,5-tris( N -phenylbenzimidazol-2-yl)benzene (TPBi, see FIG. 7) They were sequentially deposited at a rate of 0.1 nm/s at a pressure of 1x10 ^-6 torr to form an exciton blocking layer and an electron transport layer of 5 nm and 30 nm, respectively.

Then, as an electron injection material, LiF was deposited at a pressure of 1x10 ^-6 torr at a rate of 0.01 nm/s to form an electron injection layer of 1 nm.

Then, Al was deposited at a rate of 0.5 nm/sec under a pressure of 1x10 ^-6 torr to form a 100 nm cathode, thereby forming an organic light emitting diode. After device formation, the device was sealed using a CaO desiccant and a glass cover glass.

( Example 2) to ( Example 4)

An organic light emitting diode was manufactured in the same manner as in Example 1, except that the compound shown in Table 1 was used as a host material.

( comparative example One)

An organic light emitting diode was manufactured in the same manner as in Example 1, except that DPEPO (see FIG. 8) was used as a host material.

The electroluminescence characteristics were measured by applying a forward bias DC voltage to the organic electroluminescent devices manufactured according to Examples 1 to 4 and Comparative Example 1, and the evaluation results of the manufactured devices are shown in Table 1 below.

light emitting layer
(host) drive voltage
(V)

(%)

(%) luminance
(

) current density
(

) color coordinates
(x:y) Comparative Example 1 DPEPO 3.5 14.7 8015 16.5 0.16:0.20 Example 1 P-1 3.6 14.9 8057 19.8 0.16:0.21 Example 2 P-3 3.5 14.8 8102 45.2 0.15:0.19 Example 3 P-8 3.7 15.1 8402 67.2 0.16:0.21 Example 4 P-14 3.6 15.2 9251 69.3 0.16:0.20

As can be seen from the results in Table 1, when the organic light emitting diode was manufactured using the compound of the present invention, the luminous efficiency and luminance of the organic light emitting diode were significantly improved compared to the case of using Comparative Compound 1.

In addition, although the device characteristics in which the compound of the present invention is applied only to the light emitting layer has been described in the evaluation results of the above-described device fabrication, the compound of the present invention may be applied to one or more of the light emitting layer and the electron transport layer.

The above description is merely illustrative of the present invention, and those of ordinary skill in the art to which the present invention pertains include other compounds in the light emitting layer within a range that does not depart from the essential characteristics of the present invention to improve performance Various modifications are possible.

Accordingly, the embodiments disclosed in the present specification are intended to illustrate, not to limit the present invention, and the scope of the spirit of the present invention is not limited by these embodiments. The protection scope of the present invention should be construed by the following claims, and all technologies within the scope equivalent thereto should be construed as being included in the scope of the present invention.

10: anode 20: hole conductive layer
23: hole injection layer 25: hole transport layer
40: light emitting layer 50: electron conductive layer
53: electron injection layer 55: electron transport layer
70: cathode

Claims (12)

A compound characterized in that it is one of Formulas 1 to 2 below:
<Formula 1><Formula2>

The substituents (R) are each independently, a substituted or unsubstituted C ₃ -C ₃₀ heteroaryl group; Or, a substituted or unsubstituted fused arylamine group. According to claim 1, wherein the substituents (R) are each independently hydrogen, deuterium, C ₁ -C ₉ alkyl group, C ₃ -C ₃₀ cycloalkyl group, C ₆ -C ₃₀ aryl group, C ₈ -C ₃₀ of alkylaryl group, C ₈ -C ₃₀ arylalkyl group, C ₂ -C ₃₀ heteroaryl group, aryloxy group, arylamine, fused arylamine group, phosphine or phosphine oxide group, thiol group, sulfoxide Or a compound characterized in that it is further substituted with one or more substituents selected from the group consisting of a sulfone group. delete delete delete delete The compound according to claim 1, wherein the compound is one of formulas P-5 to P-10:

anode; cathode; and an organic layer formed between the anode and the cathode,
The organic layer is an organic light emitting diode, characterized in that it comprises the compound of claim 1 alone or in combination. 9. The method of claim 8,
The organic layer comprises at least one of a hole injection layer, a hole transport layer, an exciton blocking layer, a light emitting layer, an electron transport layer, and an electron injection layer. 10. The method of claim 9,
The organic layer comprises at least one of the light emitting layer and the electron transport layer. 9. The method of claim 8,
The organic layer comprises at least two stacks including a hole transport layer, a light emitting layer, and an electron transport layer sequentially formed on the anode. A display device comprising the organic light emitting diode of claim 8; and a controller for driving the display device.

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