KR102200026B1 - Compound and organic light emitting device comprising the same - Google Patents

Abstract

The present specification provides a compound of Formula 1 and an organic light emitting device including the same.

Description

Compound and organic light-emitting device comprising the same TECHNICAL FIELD

The present specification relates to a compound and an organic light emitting device including the same.

This specification claims the interests of the filing date of the Korean Patent Application No. 10-2018-0045018 filed with the Korean Intellectual Property Office on April 18, 2018, all of the contents of which are incorporated herein.

The organic light emitting device has a structure in which an organic thin film is disposed between two electrodes. When a voltage is applied to the organic light-emitting device having such a structure, electrons and holes injected from the two electrodes are combined in the organic thin film to form a pair and then emit light while disappearing. The organic thin film may be composed of a single layer or multiple layers as necessary.

The material of the organic thin film may have a light emitting function if necessary. For example, as the organic thin film material, a compound capable of constituting a light emitting layer by itself may be used, or a compound capable of serving as a host or a dopant of the host-dopant-based light emitting layer may be used. In addition, as a material of the organic thin film, a compound capable of performing a role of hole injection, hole transport, electron blocking, hole blocking, electron transport, or electron injection may be used.

In order to improve the performance, life, or efficiency of an organic light emitting device, the development of a material for an organic thin film is continuously required.

International Patent Application Publication No. 2003-012890

The present specification provides a compound and an organic light emitting device including the same.

An exemplary embodiment of the present specification provides a compound represented by Formula 1 below.

[Formula 1]

In Formula 1,

X is O or S,

At least one of R3, R6, and R10 to R15 is represented by the following formula (2),

[Formula 2]

At least one of R1 to R16 to which Formula 2 is not bonded is represented by the following Formula 3,

[Formula 3]

In Formulas 2 and 3,

L1 and L2 are the same as or different from each other, and each independently a direct bond; A substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,

k is an integer of 1 to 3, and when k is 2 or more, L1 is the same as or different from each other,

m is an integer of 1 to 3, and when m is 2 or more, L2 is the same as or different from each other,

The rest of R1 to R16 are hydrogen,

R17 is the same as or different from each other, and each independently a substituted or unsubstituted aryl group,

n is an integer of 0 to 9, and when n is 2 or more, R17 is the same as or different from each other.

In addition, the present application is a first electrode; A second electrode provided to face the first electrode; And one or more organic material layers provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes the aforementioned compound.

The compound according to the exemplary embodiment of the present application is used in an organic light-emitting device, thereby lowering a driving voltage of the organic light-emitting device, improving light efficiency, and improving lifespan characteristics of the device by thermal stability of the compound.

1 shows an example of an organic light emitting device in which a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4 are sequentially stacked.
2 is an organic light emitting diode in which a substrate (1), an anode (2), a hole injection layer (5), a hole transport layer (6), a light emitting layer (3), an electron injection and transport layer (7), and a cathode (4) are sequentially stacked. It shows an example of the device.

Hereinafter, the present specification will be described in more detail.

The present specification provides a compound represented by Chemical Formula 1.

When the compound represented by Formula 1 according to the present specification is used in an organic light-emitting device, electrons are delocalized with an appropriate intensity to exhibit excellent performance in efficiency, driving voltage, stability, etc., and excellent thermal stability. In addition, when the nitrile group of Formula 2 is included, it exhibits excellent properties by having a deep HOMO level and major stability, and when the anthracene group of Formula 3 is included, the glass transition temperature (Tg) is increased, thereby providing excellent thermal stability.

Examples of the substituent in the present specification are described below, but are not limited thereto.

The term "substituted" means that the hydrogen atom bonded to the carbon atom of the compound is replaced with another substituent, and the position to be substituted is not limited as long as the position where the hydrogen atom is substituted, that is, the position where the substituent can be substituted, and when two or more are substituted , Two or more substituents may be the same or different from each other.

In the present specification, the term "substituted or unsubstituted" refers to deuterium; Halogen group; Nitrile group; Nitro group; Alkyl group; Cycloalkyl group; Silyl group; Amine group; Aryl group; And it is substituted with one or two or more substituents selected from the group consisting of a heterocyclic group, two or more of the substituents exemplified above are substituted with a connected substituent, or does not have any substituents. For example, "a substituent to which two or more substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group or may be interpreted as a substituent to which two phenyl groups are connected.

In the present specification, examples of the halogen group include fluorine, chlorine, bromine or iodine.

In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 50. Specific examples include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl , Isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n -Heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethyl Heptyl, 1-ethylpropyl, 1,1-dimethylpropyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, and the like, but are not limited thereto.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 30 carbon atoms, and specifically, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, etc., but are limited thereto. It is not.

In the present specification, the silyl group is specifically trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, phenylsilyl group, etc. However, it is not limited thereto.

In the present specification, the amine group is -NH ₂ ; Monoalkylamine group; Dialkylamine group; N-alkylarylamine group; Monoarylamine group; Diarylamine group; N-arylheteroarylamine group; It may be selected from the group consisting of an N-alkylheteroarylamine group, a monoheteroarylamine group, and a diheteroarylamine group, and the number of carbon atoms is not particularly limited, but is preferably 1 to 30. Specific examples of the amine group include methylamine group, dimethylamine group, ethylamine group, diethylamine group, phenylamine group, naphthylamine group, biphenylamine group, anthracenylamine group, 9-methyl-anthracenylamine group , Diphenylamine group, ditolylamine group, N-phenyltolylamine group, triphenylamine group, N-phenylbiphenylamine group; N-phenylnaphthylamine group; N-biphenylnaphthylamine group; N-naphthylfluorenylamine group; N-phenylphenanthrenylamine group; N-biphenylphenanthrenylamine group; N-phenylfluorenylamine group; N-phenylterphenylamine group; N-phenanthrenylfluorenylamine group; N-biphenylfluorenylamine group, and the like, but are not limited thereto.

In the present specification, when the aryl group is a monocyclic aryl group, the number of carbon atoms is not particularly limited, but it is preferably 6 to 30 carbon atoms. Specifically, the monocyclic aryl group may be a phenyl group, a biphenyl group, or a terphenyl group, but is not limited thereto.

When the aryl group is a polycyclic aryl group, the number of carbon atoms is not particularly limited. It is preferably 10 to 24 carbon atoms. Specifically, the polycyclic aryl group may be a naphthyl group, an anthracene group, a phenanthrene group, a pyrenyl group, a perylenyl group, a chrysene group, a fluorene group, and the like, but is not limited thereto.

In the present specification, the heterocyclic group is an atom other than carbon and contains one or more heteroatoms, and specifically, the heteroatoms may contain one or more atoms selected from the group consisting of O, N, Se, Si, and S. have. The number of carbon atoms of the heterocyclic group is not particularly limited, but is preferably 2 to 60 carbon atoms or 2 to 30 carbon atoms. Examples of the heterocyclic group include thiophene group, furan group, pyrrole group, imidazolyl group, thiazolyl group, oxazolyl group, oxadiazolyl group, triazolyl group, pyridyl group, bipyridyl group, pyrimidyl group, tria Genyl group, acridyl group, pyridazinyl group, pyrazinyl group, quinolinyl group, quinazolinyl group, quinoxalinyl group, phthalazinyl group, pyridopyrimidinyl group, pyridopyrazinyl group, pyrazinopyrazinyl group , Isoquinolinyl group, indole group, carbazolyl group, benzoxazolyl group, benzimidazolyl group, benzothiazolyl group, benzocarbazolyl group, dibenzocarbazolyl group, benzothiophene group, dibenzothiophene group , Benzofuran group, dibenzofuran group, benzosilol group, dibenzosilol group, phenanthrolinyl group, isoxazolyl group, thiadiazolyl group, phenothiazinyl group, phenoxazine group, and condensation structures thereof, etc. However, it is not limited to these.

In the present specification, an arylene group means that the aryl group has two bonding positions, that is, a divalent group. Except that each of these is a divalent group, the description of the aryl group described above may be applied.

In the present specification, the heteroarylene group refers to a heterocyclic group having two bonding positions, that is, a divalent group. Except that each of these is a divalent group, the description of the aforementioned heterocyclic group may be applied.

In the exemplary embodiment of the present specification, L1 and L2 are the same as or different from each other, and each independently a direct bond; A substituted or unsubstituted arylene group having 6 to 30 carbon atoms; Or a substituted or unsubstituted C 3 to C 30 heteroarylene group.

In the exemplary embodiment of the present specification, L1 and L2 are the same as or different from each other, and each independently a direct bond; A substituted or unsubstituted phenylene group; A substituted or unsubstituted biphenylylene group; A substituted or unsubstituted terphenylylene group; A substituted or unsubstituted quarterphenylylene group; A substituted or unsubstituted naphthylene group; A substituted or unsubstituted anthracenylylene group; A substituted or unsubstituted divalent phenanthrene group; A substituted or unsubstituted divalent triphenylene group; A substituted or unsubstituted divalent pyrene group; A substituted or unsubstituted divalent fluorene group; A substituted or unsubstituted divalent spirofluorene group; A substituted or unsubstituted divalent dibenzothiophene group; A substituted or unsubstituted divalent dibenzofuran group; Or a substituted or unsubstituted divalent carbazole group.

In the exemplary embodiment of the present specification, L1 and L2 are the same as or different from each other, and each independently a direct bond; A phenylene group unsubstituted or substituted with an aryl group or an alkyl group; Biphenylylene group unsubstituted or substituted with an aryl group or an alkyl group; A terphenylylene group unsubstituted or substituted with an aryl group or an alkyl group; Quarterphenylylene group unsubstituted or substituted with an aryl group or an alkyl group; A naphthylene group unsubstituted or substituted with an aryl group or an alkyl group; An anthracenylylene group unsubstituted or substituted with an aryl group or an alkyl group; A divalent phenanthrene group unsubstituted or substituted with an aryl group or an alkyl group; A divalent triphenylene group unsubstituted or substituted with an aryl group or an alkyl group; A divalent pyrene group unsubstituted or substituted with an aryl group or an alkyl group; A divalent fluorene group unsubstituted or substituted with an aryl group or an alkyl group; A divalent spirofluorene group unsubstituted or substituted with an aryl group or an alkyl group; A divalent dibenzothiophene group unsubstituted or substituted with an aryl group or an alkyl group; A divalent dibenzofuran group unsubstituted or substituted with an aryl group or an alkyl group; Or a divalent carbazole group unsubstituted or substituted with an aryl group or an alkyl group.

In the exemplary embodiment of the present specification, L1 and L2 are the same as or different from each other, and each independently a direct bond; A phenylene group unsubstituted or substituted with a methyl group or a phenyl group; A biphenylylene group unsubstituted or substituted with a methyl group or a phenyl group; A terphenylylene group unsubstituted or substituted with a methyl group or a phenyl group; A quarterphenylylene group unsubstituted or substituted with a methyl group or a phenyl group; A naphthylene group unsubstituted or substituted with a methyl group or a phenyl group; An anthracenylylene group unsubstituted or substituted with a methyl group or a phenyl group; A divalent phenanthrene group unsubstituted or substituted with a methyl group or a phenyl group; A divalent triphenylene group unsubstituted or substituted with a methyl group or a phenyl group; A divalent pyrene group unsubstituted or substituted with a methyl group or a phenyl group; A divalent fluorene group unsubstituted or substituted with a methyl group or a phenyl group; A divalent spirofluorene group unsubstituted or substituted with a methyl group or a phenyl group; A divalent dibenzothiophene group unsubstituted or substituted with a methyl group or a phenyl group; A divalent dibenzofuran group unsubstituted or substituted with a methyl group or a phenyl group; Or a divalent carbazole group unsubstituted or substituted with a methyl group or a phenyl group.

In the exemplary embodiment of the present specification, L1 and L2 are the same as or different from each other, and each independently a direct bond; Phenylene group; Biphenylylene group; Terphenylylene group; Quarter phenylylene group; Naphthylene group; Anthracenylylene group; A divalent phenanthren group; Divalent triphenylene group; Divalent pyrene group; A divalent fluorene group unsubstituted or substituted with a methyl group or a phenyl group; Divalent spirofluorene group; Divalent dibenzothiophene group; Divalent dibenzofuran group; Or a divalent carbazole group unsubstituted or substituted with a phenyl group.

In the exemplary embodiment of the present specification, L1 and L2 are the same as or different from each other, and each independently a direct bond; Or it is selected from the following structural formula.

In the exemplary embodiment of the present specification, L1 and L2 are the same as or different from each other, and each independently a direct bond; Phenylene group; Or a biphenylene group.

In the exemplary embodiment of the present specification, L1 and L2 are the same as or different from each other, and each independently a direct bond; Or a phenylene group.

In the exemplary embodiment of the present specification, L1 is a phenylene group.

In the exemplary embodiment of the present specification, L1 is a direct bond.

In the exemplary embodiment of the present specification, L2 is a phenylene group.

In the exemplary embodiment of the present specification, L2 is a direct bond.

In the exemplary embodiment of the present specification, L1 and L2 are direct bonds.

In the exemplary embodiment of the present specification, X is O.

In the exemplary embodiment of the present specification, X is S.

In an exemplary embodiment of the present specification, at least one of R3, R6, and R10 to R15 is represented by Chemical Formula 2.

In an exemplary embodiment of the present specification, at least one of R3 and R6 is represented by Chemical Formula 2, and at least one of R9 to R16 is represented by Chemical Formula 3.

In an exemplary embodiment of the present specification, at least one of R10 to R12 is represented by Chemical Formula 2, and at least one of R1 to R8 is represented by Chemical Formula 3.

In the exemplary embodiment of the present specification, R3 is represented by Formula 2, and at least one of R5 to R8 is represented by Formula 3.

In the exemplary embodiment of the present specification, R6 is represented by Formula 2, and at least one of R5 to R8 is represented by Formula 3.

In an exemplary embodiment of the present specification, at least one of R10 to R12 is represented by Formula 2, and at least one of R13 to R16 is represented by Formula 3.

In an exemplary embodiment of the present specification, the remaining R1 to R16 other than Chemical Formula 2 or Chemical Formula 3 are hydrogen.

In the exemplary embodiment of the present specification, R17 is a substituted or unsubstituted aryl group.

In the exemplary embodiment of the present specification, R17 is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms.

In the exemplary embodiment of the present specification, R17 is a substituted or unsubstituted phenyl group; A substituted or unsubstituted biphenyl group; A substituted or unsubstituted terphenyl group; A substituted or unsubstituted naphthyl group; A substituted or unsubstituted pyrene group; A substituted or unsubstituted triphenylene group; Or a substituted or unsubstituted phenanthrene group.

In the exemplary embodiment of the present specification, R17 is a phenyl group unsubstituted or substituted with an aryl group; A biphenyl group unsubstituted or substituted with an aryl group; A naphthyl group unsubstituted or substituted with an aryl group; Terphenyl group unsubstituted or substituted with an aryl group; A pyrene group unsubstituted or substituted with an aryl group; Triphenylene group unsubstituted or substituted with an aryl group; Or a phenanthrene group unsubstituted or substituted with an aryl group.

In the exemplary embodiment of the present specification, R17 is a phenyl group unsubstituted or substituted with a phenyl group; A biphenyl group unsubstituted or substituted with a phenyl group; A naphthyl group unsubstituted or substituted with a phenyl group; A terphenyl group unsubstituted or substituted with a phenyl group; A pyrene group unsubstituted or substituted with a phenyl group; A triphenylene group unsubstituted or substituted with a phenyl group; Or a phenanthrene group unsubstituted or substituted with a phenyl group.

In the exemplary embodiment of the present specification, R17 is a phenyl group; Biphenyl group; A naphthyl group unsubstituted or substituted with a phenyl group; Terphenyl group; Pyren group; Triphenylene group; Or phenanthren group.

In the exemplary embodiment of the present specification, n is an integer of 1 to 3, and R17 is the same as or different from each other, and each independently a substituted or unsubstituted aryl group.

In the exemplary embodiment of the present specification, n is an integer of 1 to 3, and R17 is the same as or different from each other, and each independently a substituted or unsubstituted phenyl group; A substituted or unsubstituted biphenyl group; A substituted or unsubstituted terphenyl group; A substituted or unsubstituted naphthyl group; A substituted or unsubstituted pyrene group; A substituted or unsubstituted triphenylene group; Or a substituted or unsubstituted phenanthrene group.

In an exemplary embodiment of the present specification, the compound represented by Formula 1 is selected from the following structural formulas.

The compound according to an exemplary embodiment of the present application may be prepared by a manufacturing method described below.

For example, the compound of Formula 1 may have a core structure as shown in Schemes 1-1, 1-2, 2, and 3 below. Substituents may be combined by methods known in the art, and the type, position or number of substituents may be changed according to techniques known in the art.

[Reaction Scheme 1-1]

[Scheme 1-2]

[Scheme 2]

[Scheme 3]

In Reaction Schemes 1-1, 1-2, 2 and 3, the definitions of X, L1, L2, R17, k and m are the same as those of Formula 1, Y1 and Y2 are halogen groups, and the bond of the substituents The compound of the present specification can be prepared by changing the position and type.

In addition, the present specification provides an organic light-emitting device including the above-described compound.

In the exemplary embodiment of the present application, the first electrode; A second electrode provided to face the first electrode; And one or more organic material layers provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes the compound.

When a member is referred to herein as being “on” another member, this includes not only the case where a member is in contact with another member, but also the case where another member exists between the two members.

In the present specification, when a part "includes" a certain component, it means that other components may be further included rather than excluding other components unless specifically stated to the contrary.

The organic material layer of the organic light emitting device of the present application may have a single-layer structure, but may have a multilayer structure in which two or more organic material layers are stacked. For example, as a representative example of the organic light emitting device of the present invention, the organic light emitting device may have a structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like as an organic material layer. However, the structure of the organic light emitting device is not limited thereto and may include a smaller number of organic layers.

In the exemplary embodiment of the present application, the organic material layer includes an emission layer, and the emission layer includes the compound.

In the exemplary embodiment of the present application, the organic material layer includes a hole injection layer or a hole transport layer, and the hole injection layer or the hole transport layer includes the compound.

In the exemplary embodiment of the present application, the organic material layer includes a hole injection layer, a hole transport layer, or a hole injection and transport layer, and the hole injection layer, a hole transport layer, or a hole injection and transport layer includes the compound.

In the exemplary embodiment of the present application, the organic material layer includes an electron transport layer or an electron injection layer, and the electron transport layer or the electron injection layer includes the compound.

In the exemplary embodiment of the present application, the organic material layer includes an electron injection layer, an electron transport layer, or an electron injection and transport layer, and the electron injection layer, the electron transport layer, or the electron injection and transport layer includes the compound.

In the exemplary embodiment of the present application, the organic light-emitting device includes: a first electrode; A second electrode provided to face the first electrode; And a light emitting layer provided between the first electrode and the second electrode. It includes two or more organic material layers provided between the emission layer and the first electrode, or between the emission layer and the second electrode, and at least one of the organic material layers of the two or more layers includes the compound.

In the exemplary embodiment of the present application, the organic material layer further includes a hole injection layer or a hole transport layer including a compound including an arylamino group, carbazolyl group, or benzocarbazolyl group in addition to the organic material layer including the compound.

In another exemplary embodiment, the organic light emitting device may be an organic light emitting device having a structure (normal type) in which an anode, one or more organic material layers, and a cathode are sequentially stacked on a substrate.

In another embodiment, the organic light-emitting device may be an inverted type organic light-emitting device in which a cathode, one or more organic material layers, and an anode are sequentially stacked on a substrate.

For example, the structure of an organic light-emitting device according to an exemplary embodiment of the present application is illustrated in FIGS. 1 and 2.

1 illustrates a structure of an organic light emitting device in which a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4 are sequentially stacked. In this structure, the compound may be included in the light emitting layer 3.

2 is an organic light emitting diode in which a substrate (1), an anode (2), a hole injection layer (5), a hole transport layer (6), a light emitting layer (3), an electron injection and transport layer (7), and a cathode (4) are sequentially stacked. The structure of the device is illustrated. In such a structure, the compound may be included in one or more of the hole injection layer 5, the hole transport layer 6, the emission layer 3, and the electron injection and transport layer 7.

The organic light-emitting device of the present application may be manufactured by materials and methods known in the art, except that at least one of the organic material layers includes the compound of the present application, that is, the compound.

When the organic light emitting device includes a plurality of organic material layers, the organic material layers may be formed of the same material or different materials.

For example, the organic light-emitting device of the present application may be manufactured by sequentially laminating a first electrode, an organic material layer, and a second electrode on a substrate. At this time, using a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation, a metal or conductive metal oxide or alloy thereof is deposited on the substrate to form an anode. And, after forming an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer thereon, it can be prepared by depositing a material that can be used as a cathode thereon. In addition to this method, an organic light emitting device may be manufactured by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate.

In addition, the compound of Formula 1 may be formed as an organic material layer by a solution coating method as well as a vacuum deposition method when manufacturing an organic light emitting device. Here, the solution coating method refers to spin coating, dip coating, doctor blading, inkjet printing, screen printing, spray method, roll coating, and the like, but is not limited thereto.

In addition to this method, an organic light emitting device may be manufactured by sequentially depositing an organic material layer and an anode material from a cathode material on a substrate (International Patent Application Publication No. 2003/012890). However, the manufacturing method is not limited thereto.

In the exemplary embodiment of the present application, the first electrode is an anode, and the second electrode is a cathode.

In another exemplary embodiment, the first electrode is a cathode, and the second electrode is an anode.

As the anode material, a material having a large work function is preferable so that holes can be smoothly injected into the organic material layer. Specific examples of the cathode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); A combination of a metal and an oxide such as ZnO:Al or SnO ₂ :Sb; Poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), conductive polymers such as polypyrrole and polyaniline, and the like, but are not limited thereto.

It is preferable that the cathode material is a material having a small work function to facilitate electron injection into the organic material layer. Specific examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof; There are multi-layered materials such as LiF/Al or LiO ₂ /Al, but are not limited thereto.

The hole injection layer is a layer that injects holes from the electrode, and has the ability to transport holes as a hole injection material, and thus has a hole injection effect at the anode, an excellent hole injection effect for the light emitting layer or the light emitting material, and is generated from the light emitting layer. A compound that prevents the movement of excitons to the electron injection layer or the electron injection material and has excellent ability to form a thin film is preferable. It is preferable that the HOMO (highest occupied molecular orbital) of the hole injection material is between the work function of the positive electrode material and the HOMO of the surrounding organic material layer. Specific examples of hole injection materials include metal porphyrin, oligothiophene, arylamine-based organic substances, hexanitrile hexaazatriphenylene-based organic substances, quinacridone-based organic substances, and perylene-based organic substances. Organic substances, anthraquinone, polyaniline, and polythiophene-based conductive polymers, but are not limited thereto.

The hole transport layer is a layer that receives holes from the hole injection layer and transports holes to the emission layer, and the hole transport material is a material capable of transporting holes from the anode or the hole injection layer to the emission layer, and has high mobility for holes. The material is suitable. Specific examples include an arylamine-based organic material, a conductive polymer, and a block copolymer including a conjugated portion and a non-conjugated portion, but are not limited thereto.

The light-emitting material is a material capable of emitting light in a visible light region by transporting and bonding holes and electrons from the hole transport layer and the electron transport layer, respectively, and a material having good quantum efficiency for fluorescence or phosphorescence is preferable. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq ₃ ); Carbazole-based compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzo quinoline-metal compound; Benzoxazole, benzthiazole, and benzimidazole-based compounds; Poly(p-phenylenevinylene) (PPV)-based polymer; Spiro compounds; Polyfluorene, rubrene, and the like, but are not limited thereto.

The emission layer may include a host material and a dopant material. Host materials include condensed aromatic ring derivatives or heterocyclic-containing compounds. Specifically, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, and fluoranthene compounds, and heterocycle-containing compounds include compounds, dibenzofuran derivatives, and ladder furan compounds. , Pyrimidine derivatives, and the like, but are not limited thereto.

The electron transport layer is a layer that receives electrons from the electron injection layer and transports electrons to the emission layer.As an electron transport material, a material capable of injecting electrons well from the cathode and transferring them to the emission layer, and a material having high mobility for electrons is suitable. Do. Specific examples include the Al complex of 8-hydroxyquinoline; Complexes containing Alq ₃ ; Organic radical compounds; Hydroxyflavone-metal complexes and the like, but are not limited thereto. The electron transport layer can be used with any desired cathode material as used according to the prior art. In particular, examples of suitable cathode materials are conventional materials that have a low work function and are followed by an aluminum layer or a silver layer. Specifically, they are cesium, barium, calcium, ytterbium, and samarium, and in each case an aluminum layer or a silver layer follows.

The electron injection layer is a layer that injects electrons from the electrode, has the ability to transport electrons, has an electron injection effect from the cathode, an excellent electron injection effect on the light emitting layer or light emitting material, and injects holes of excitons generated from the light emitting layer. A compound that prevents migration to the layer and has excellent thin film formation ability is preferable. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylene tetracarboxylic acid, preorenylidene methane, anthrone, etc. Complex compounds and nitrogen-containing 5-membered cyclic derivatives, but are not limited thereto.

Examples of the metal complex compound include lithium 8-hydroxyquinolinato, bis(8-hydroxyquinolinato)zinc, bis(8-hydroxyquinolinato)copper, bis(8-hydroxyquinolinato)manganese, Tris(8-hydroxyquinolinato)aluminum, tris(2-methyl-8-hydroxyquinolinato)aluminum, tris(8-hydroxyquinolinato)gallium, bis(10-hydroxybenzo[h] Quinolinato)beryllium, bis(10-hydroxybenzo[h]quinolinato)zinc, bis(2-methyl-8-quinolinato)chlorogallium, bis(2-methyl-8-quinolinato)( o-cresolato)gallium, bis(2-methyl-8-quinolinato)(1-naphtholato)aluminum, bis(2-methyl-8-quinolinato)(2-naphtholato)gallium, etc. It is not limited to this.

The hole blocking layer is a layer that prevents holes from reaching the cathode, and may be generally formed under the same conditions as the hole injection layer. Specifically, there are oxadiazole derivatives, triazole derivatives, phenanthroline derivatives, BCP, aluminum complexes, etc., but are not limited thereto.

The organic light emitting device according to the present specification may be a top emission type, a bottom emission type, or a double-sided emission type depending on the material used.

Preparation of the compound represented by Formula 1 and the organic light emitting device including the same will be described in detail in the following Examples. However, the following examples are for illustrative purposes only, and the scope of the present specification is not limited thereto.

<Production Example>

Example 1 (E1)

After completely dissolving the compound represented by the formula E1-P1-A (20g, 44.9mmol) and the zinc cyanide compound (2.6g, 22.4mmol) in dimethylacetamide (200mL), tetrakistriphenyl-phos After adding pinopalladium (1.6g, 1.34mmol), the mixture was heated and stirred for 2 hours. After lowering the temperature to room temperature and terminating the reaction, 200 ml of water was added thereto, and the white solid was filtered. The filtered white solid was washed twice with ethanol and water, respectively, to prepare a compound (14.1g, yield 80%) represented by the formula E1-P1.

MS [M+H] ⁺ = 392

After completely dissolving the compound represented by the formula E1-P1 (14g, 35.7mmol) and the compound of the formula E1-P2-A (10.0g, 39.3mmol) in Dioxane (140mL), potassium acetate (10.5g, 107.2mmol) was added, followed by heating and stirring. After lowering the temperature to room temperature and terminating the reaction, the potassium carbonate solution was removed and filtered to remove potassium acetate. The filtrate was solidified with ethanol and filtered. The white solid was washed twice with ethanol each to prepare a compound (15.5g, yield 90%) represented by the formula E1-P2.

MS [M+H] ⁺ = 484

After completely dissolving the compound represented by Formula E1-P2 (10g, 20.7mmol) and the compound represented by Formula E1-P3-A (8.5, 20.7mmol) in tetrahydrofuran (THF) (100mL), potassium carbonate (8.6 g, 62.1 mmol) was dissolved in 40 mL of water and added. After tetrakistriphenyl-phosphinopalladium (0.7g, 0.621mmol) was added, the mixture was heated and stirred for 8 hours. After lowering the temperature to room temperature and terminating the reaction, the potassium carbonate solution was removed and a white solid was filtered. The filtered white solid was washed twice with THF and ethyl acetate, respectively, to prepare a compound represented by Formula E1 (9.5, yield 70%).

MS [M+H] ⁺ = 686

Example 2 (E2)

A compound represented by the formula E2-P1 was prepared in the same manner as in the preparation method of E1-P1 of Example 1, except that each starting material was used in the above reaction scheme.

MS [M+H] ⁺ = 392

A compound represented by the formula E2-P2 was prepared in the same manner as in the preparation method of E1-P2 of Example 1, except that each starting material was used in the above reaction scheme.

MS [M+H] ⁺ = 484

A compound represented by Formula E2 was prepared in the same manner as in Example 1, except that each starting material was used as in the above reaction formula.

MS [M+H] ⁺ = 660

Example 3 (E3)

A compound represented by Formula E3-P1 was prepared in the same manner as in Example 1, except that each starting material was used in the above reaction scheme.

MS [M+H] ⁺ = 392

A compound represented by Formula E3-P2 was prepared in the same manner as in Example 1 of E1-P2, except that each starting material was represented by the above reaction formula.

MS [M+H] ⁺ = 484

A compound represented by Formula E3 was prepared in the same manner as in the preparation method of E1 of Example 1, except that each starting material was used in the above reaction scheme.

MS [M+H] ⁺ = 762

Example 4 (E4)

A compound represented by Formula E4-P1 was prepared in the same manner as in the method of preparing E1-P1 of Example 1, except that each starting material was represented by the above reaction scheme.

MS [M+H] ⁺ = 468

A compound represented by Formula E4-P2 was prepared in the same manner as in Example 1 of E1-P2, except that each starting material was represented by the above reaction scheme.

MS [M+H] ⁺ = 484

A compound represented by Formula E4 was prepared in the same manner as in Example 1, except that each starting material was used in the above reaction scheme.

MS [M+H] ⁺ = 686

Example 5 (E5)

A compound represented by Formula E5-P1 was prepared in the same manner as in the preparation method of E1-P1 of Example 1, except that each starting material was used as in the above reaction scheme.

MS [M+H] ⁺ = 392

A compound represented by Formula E5-P2 was prepared in the same manner as in Example 1 of E1-P2, except that each starting material was represented by the above reaction scheme.

MS [M+H] ⁺ = 484

A compound represented by Formula E5 was prepared in the same manner as in the preparation method of E1 of Example 1, except that each starting material was used in the above reaction scheme.

MS [M+H] ⁺ = 610

Example 6 (E6)

A compound represented by Formula E6 was prepared in the same manner as in the preparation method of E1 of Example 1, except that each starting material was used in the above reaction formula.

MS [M+H] ⁺ = 660

Example 7 (E7)

A compound represented by Chemical Formula E7 was prepared in the same manner as in the method for preparing E1 of Example 1, except that each starting material was used in the above reaction formula.

MS [M+H] ⁺ = 686

Example 8 (E8)

A compound represented by Formula E8-P1 was prepared in the same manner as in the preparation method of E1-P1 of Example 1, except that each starting material was used in the above reaction scheme.

MS [M+H] ⁺ = 408

A compound represented by Formula E8-P2 was prepared in the same manner as in Example 1 of E1-P2, except that each starting material was used in the above reaction scheme.

MS [M+H] ⁺ = 500

A compound represented by Chemical Formula E8 was prepared in the same manner as in the method for preparing E1 of Example 1, except that each starting material was as described in the reaction scheme.

MS [M+H] ⁺ = 752

Example 9 (E9)

A compound represented by Formula E9-P1 was prepared in the same manner as in Example 1 of E4-P1, except that each starting material was represented by the above reaction formula.

MS [M+H] ⁺ = 484

A compound represented by Formula E9-P2 was prepared in the same manner as in Example 1 of E1-P2, except that each starting material was represented by the above reaction scheme.

MS [M+H] ⁺ = 576

A compound represented by Formula E9 was prepared in the same manner as in the preparation method of E1 of Example 1, except that each starting material was used in the above reaction scheme.

MS [M+H] ⁺ = 702

Example 10 (E10)

A compound represented by Formula E10-P1 was prepared in the same manner as in the preparation method of E1-P1 of Example 1, except that each starting material was used in the above reaction scheme.

MS [M+H] ⁺ = 408

A compound represented by Formula E10-P2 was prepared in the same manner as in Example 1 of E1-P2, except that each starting material was represented by the above reaction formula.

MS [M+H] ⁺ = 500

A compound represented by Formula E10 was prepared in the same manner as in Example 1, except for using each starting material as in the above reaction formula.

MS [M+H] ⁺ = 702

Example 11 (E11)

A compound represented by Formula E11-P1 was prepared in the same manner as in the preparation method of E1-P1 of Example 1, except that each starting material was used in the above reaction scheme.

MS [M+H] ⁺ = 408

A compound represented by Formula E11-P2 was prepared in the same manner as in Example 1 of E1-P2, except that each starting material was used in the above reaction scheme.

MS [M+H] ⁺ = 500

A compound represented by Formula E11 was prepared in the same manner as in Example 1, except that each starting material was used in the above reaction scheme.

MS [M+H] ⁺ = 752

Example 12 (E12)

A compound represented by Formula E12-P1 was prepared in the same manner as in the preparation method of E1-P1 of Example 1, except that each starting material was represented by the above reaction formula.

MS [M+H] ⁺ = 408

A compound represented by Formula E12-P2 was prepared in the same manner as in Example 1, except that each starting material was used in the above reaction scheme.

MS [M+H] ⁺ = 500

A compound represented by Chemical Formula E12 was prepared in the same manner as in the preparation method of E1 of Example 1, except that each starting material was used in the above reaction formula.

MS [M+H] ⁺ = 626

Example 13 (E13)

A compound represented by Chemical Formula E13 was prepared in the same manner as in the preparation method of E1 of Example 1, except that each starting material was used in the above reaction formula.

MS [M+H] ⁺ = 702

Example 14 (E14)

A compound represented by Formula E14 was prepared in the same manner as in Example 1, except for using each starting material as in the above reaction formula.

MS [M+H] ⁺ = 610

Example 15 (E15)

A compound represented by Chemical Formula E15 was prepared in the same manner as in the preparation method of E1 of Example 1, except that each starting material was used as in the reaction scheme.

MS [M+H] ⁺ = 702

Experimental Example 1-1

A glass substrate coated with a thin film of 1000 Å of indium tin oxide (ITO) was put in distilled water dissolved in a detergent and washed with ultrasonic waves. At this time, a product made by Fischer Co. was used as a detergent, and distilled water secondarily filtered with a filter made by Millipore Co. was used as distilled water. After washing the ITO for 30 minutes, it was repeated twice with distilled water to perform ultrasonic cleaning for 10 minutes. After washing with distilled water, ultrasonic washing was performed with a solvent of isopropyl alcohol, acetone, and methanol, dried, and then transported to a plasma cleaner. In addition, after cleaning the substrate for 5 minutes using oxygen plasma, the substrate was transported to a vacuum evaporator.

On the thus prepared ITO transparent electrode, the following HI-A compound was thermally vacuum deposited to a thickness of 600Å to form a hole injection layer. The following HAT compound 50Å and the following HT-A compound 60Å were sequentially vacuum-deposited on the hole injection layer to form a hole transport layer.

Subsequently, the following BH compound and BD compound with a film thickness of 20 nm were vacuum deposited on the hole transport layer at a weight ratio of 25:1 to form a light emitting layer.

On the emission layer, the compound (E1) of Example 1 and the following LiQ compound were vacuum-deposited at a weight ratio of 1:1 to form an electron injection and transport layer with a thickness of 350Å. Lithium fluoride (LiF) in a thickness of 10 Å and aluminum in a thickness of 1000 Å were sequentially deposited on the electron injection and transport layer to form a negative electrode.

Was maintained at the deposition rate of the organic material in the above process, 0.4 to 0.9 Å / sec, the lithium fluoride of the cathode was 0.3Å / sec, aluminum was deposited at a rate of 2Å / sec, the degree of vacuum during the deposition to 1Х10 ^-7 By maintaining 5Х10 ^-5 torr, an organic light emitting device was manufactured.

Experimental Examples 1-2 to 1-15

An organic light emitting device was manufactured in the same manner as in Experimental Example 1-1, except that the compounds of Examples 2 to 15 (E2 to E15) were used instead of the compound (E1) of Example 1.

Comparative Examples 1-1 to 1-14

An organic light-emitting device was manufactured in the same manner as in Experimental Example 1-1, except that the compounds (ET-A to ET-N) were used instead of the compound (E1) of Example 1.

The driving voltage and luminous efficiency were measured at a current density of 10 mA/cm ² for the organic light emitting device prepared in the above Experimental Examples and Comparative Examples, and the time at which it becomes 90% of the initial luminance at a current density of 20 mA/cm ² (T90) Was measured. The results are shown in Table 1 below.

division Voltage
(V@10 mA/cm ² ) efficiency
(cd/A@10 mA/cm ² ) Color coordinates
(x, y) Life(h)
T90 at 20 mA/cm ² ) Experimental Example 1-1 (E1) 4.00 5.11 (0.142, 0.096) 171 Experimental Example 1-2 (E2) 4.10 5.06 (0.142, 0.096) 202 Experimental Example 1-3 (E3) 4.12 5.03 (0.142, 0.096) 210 Experimental Example 1-4 (E4) 3.97 5.15 (0.142, 0.096) 168 Experimental Example 1-5 (E5) 3.99 5.10 (0.142, 0.096) 212 Experimental Example 1-6 (E6) 4.10 5.08 (0.142, 0.097) 233 Experimental Example 1-7 (E7) 4.11 4.98 (0.142, 0.096) 222 Experimental Example 1-8 (E8) 4.02 5.07 (0.142, 0.099) 234 Experimental Example 1-9 (E9) 4.08 5.03 (0.142, 0.096) 188 Experimental Example 1-10 (E10) 4.11 5.04 (0.142, 0.099) 210 Experimental Example 1-11 (E11) 3.99 5.06 (0.142, 0.096) 248 Experimental Example 1-12 (E12) 4.02 5.03 (0.142, 0.097) 250 Experimental Example 1-13 (E13) 4.13 5.00 (0.142, 0.096) 261 Experimental Example 1-14 (E14) 4.01 5.10 (0.142, 0.099) 177 Experimental Example 1-15 (E15) 4.03 5.09 (0.142, 0.096) 228 Comparative Example 1-1 (ET-A) 5.42 2.22 (0.142, 0.096) 88 Comparative Example 1-2 (ET-B) 5.10 3.45 (0.142, 0.096) 94 Comparative Example 1-3 (ET-C) 4.70 4.94 (0.142, 0.096) 28 Comparative Example 1-4 (ET-D) 4.60 4.98 (0.142, 0.096) 19 Comparative Example 1-5 (ET-E) 5.01 2.91 (0.142, 0.096) 80 Comparative Example 1-6 (ET-F) 4.98 2.00 (0.142, 0.096) 86 Comparative Example 1-7 (ET-G) 4.01 3.87 (0.142, 0.097) 77 Comparative Example 1-8 (ET-H) 4.22 3.77 (0.142, 0.097) 70 Comparative Example 1-9 (ET-I) 4.30 3.80 (0.142, 0.097) 81 Comparative Example 1-10 (ET-J) 5.00 3.01 (0.142, 0.097) 71 Comparative Example 1-11 (ET-K) 4.18 3.87 (0.142, 0.097) 277 Comparative Example 1-12 (ET-L) 4.22 3.71 (0.142, 0.097) 270 Comparative Example 1-13 (ET-M) 4.30 3.60 (0.142, 0.097) 281 Comparative Example 1-14 (ET-N) 5.00 3.31 (0.142, 0.097) 271

As shown in Table 1, the compound represented by Formula 1 according to the present invention may be used in an organic material layer capable of simultaneously injecting electrons and transporting electrons in an organic light emitting device.

When comparing Experimental Examples 1-1 to 1-7 and Experimental Examples 1-8 to 1-13 of Table 1, the effect of the two cores of spiro [fluorene-xanthene] or spiro [fluorene-thioxanthene] is distinguished. All of them are remarkably excellent in terms of driving voltage, efficiency, and lifetime of the organic light-emitting device.

Comparing the Experimental Examples of Table 1 with Comparative Examples 1-1, 1-2, 1-5, and 1-6, as in Formula 1 according to the present invention, spiro [fluorene-xanthene] or spiro [fluorene-cy] Oxanthene] is substituted with a cyano group and anthracene in terms of efficiency and lifespan of an organic light-emitting device as compared to a compound in which a cyano group is unsubstituted in spiro[fluorene-xanthene] or spiro[fluorene-thioxanthene]. Remarkably excellent.

Comparing the Experimental Examples of Table 1 and Comparative Examples 1-3 to 1-4, as shown in Formula 1 according to the present invention, a cyano group and anthracene in spiro [fluorene-xanthene] or spiro [fluorene-thioxanthene] This substituted compound is significantly superior to the compound in which anthracene is substituted with spiro[fluorene-xanthene] or spiro[fluorene-thioxanthene] in terms of the lifespan of the organic light-emitting device.

Comparing the Experimental Examples of Table 1 and Comparative Examples 1-5 to 1-6, as in Chemical Formula 1 according to the present invention, cyano groups and anthracene in spiro [fluorene-xanthene] or spiro [fluorene-thioxanthene] This substituted compound is significantly superior in terms of efficiency and lifespan of an organic light-emitting device as compared to a compound in which an aryl group other than a cyano group and an anthracene group is substituted with spiro[fluorene-xanthene] or spiro[fluorene-thioxanthene].

Comparing the Experimental Examples of Table 1 and Comparative Examples 1-7 to 1-10, as shown in Formula 1 according to the present invention, a cyano group and anthracene in spiro [fluorene-xanthene] or spiro [fluorene-thioxanthene] In this substituted compound, a substituent containing a cyano group and a substituent containing an anthracene group are bonded, but the efficiency and lifespan of an organic light-emitting device are compared to compounds whose core structure is fluorene, spirofluorene, or xanthene or dibenzothiophene. It is remarkably excellent in terms of

Comparing the Experimental Examples of Table 1 with Comparative Examples 1-11 to 1-14, R3, R6 of spiro [fluorene-xanthene] or spiro [fluorene-thioxanthene] as in Formula 1 according to the present invention, A compound in which a cyano group is substituted for R10 to R15 is remarkably excellent in terms of the efficiency of an organic light-emitting device.

1: substrate
2: anode
3: light emitting layer
4: cathode
5: hole injection layer
6: hole transport layer
7: electron injection and transport layer

Claims (13)

Compound represented by the following formula (1):
[Formula 1]

In Formula 1,
X is O or S,
At least one of R3, R6, and R10 to R15 is represented by the following formula (2),
[Formula 2]

At least one of R1 to R16 to which Formula 2 is not bonded is represented by the following Formula 3,
[Formula 3]

In Formulas 2 and 3,
L1 and L2 are the same as or different from each other, and each independently a direct bond; Or a substituted or unsubstituted arylene group having 6 to 30 carbon atoms,
k is an integer of 1 to 3, and when k is 2 or more, L1 is the same as or different from each other,
m is an integer of 1 to 3, and when m is 2 or more, L2 is the same as or different from each other,
The rest of R1 to R16 are hydrogen,
R17 is the same as or different from each other, and each independently a substituted or unsubstituted aryl group,
n is an integer of 0 to 9, and when n is 2 or more, R17 is the same as or different from each other. The method according to claim 1, wherein L1 and L2 are the same as or different from each other, and each independently a direct bond; Or a compound selected from the following structural formula:

The method according to claim 1, wherein L1 and L2 are the same as or different from each other, and each independently a direct bond; Or a phenylene group. The compound of claim 1, wherein at least one of R3 and R6 is represented by Chemical Formula 2, and at least one of R9 to R16 is represented by Chemical Formula 3. The compound of claim 1, wherein at least one of R10 to R12 is represented by Chemical Formula 2, and at least one of R1 to R8 is represented by Chemical Formula 3. The compound of claim 1, wherein R3 is represented by Chemical Formula 2, and at least one of R5 to R8 is represented by Chemical Formula 3. The compound of claim 1, wherein at least one of R10 to R12 is represented by Chemical Formula 2, and at least one of R13 to R16 is represented by Chemical Formula 3. The method according to claim 1, wherein n is an integer of 1 to 3, R17 is the same as or different from each other, and each independently a substituted or unsubstituted phenyl group; A substituted or unsubstituted biphenyl group; A substituted or unsubstituted terphenyl group; A substituted or unsubstituted naphthyl group; A substituted or unsubstituted pyrene group; A substituted or unsubstituted triphenylene group; Or a substituted or unsubstituted phenanthrene group. The compound of claim 1, wherein the compound represented by Formula 1 is selected from the following structural formulas:

A first electrode; A second electrode provided to face the first electrode; And one or more organic material layers provided between the first electrode and the second electrode, wherein at least one of the organic material layers comprises the compound according to any one of claims 1 to 9 device. The organic light-emitting device of claim 10, wherein the organic material layer comprises a hole injection layer, a hole transport layer, or a hole injection and transport layer, and the hole injection layer, a hole transport layer, or a hole injection and transport layer comprises the compound. The organic light-emitting device of claim 10, wherein the organic material layer includes an emission layer, and the emission layer includes the compound. The organic light-emitting device of claim 10, wherein the organic material layer includes an electron injection layer, an electron transport layer, or an electron injection and transport layer, and the electron injection layer, the electron transport layer, or the electron injection and transport layer includes the compound.

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