WO2020050563A1 - Organic light emitting diode - Google Patents

Abstract

The present specification relates to an organic light emitting diode comprising: a first electrode; a second electrode placed opposite to the first electrode; and a first organic layer and a second organic layer disposed between the first electrode and the second electrode, wherein the first organic layer comprises a compound represented by chemical formula 1, and the second organic layer comprises a compound represented by chemical formula 3.

Description

Organic light emitting device

This application claims the benefit of the filing date of Korean Patent Application No. 10-2018-0104682 filed with the Korea Intellectual Property Office on September 3, 2018, the entire contents of which are incorporated herein.

This specification relates to an organic light emitting device.

In general, the organic light emitting phenomenon refers to a phenomenon that converts electrical energy into light energy using an organic material. An organic light emitting device using an organic light emitting phenomenon usually has a structure including an anode and a cathode and an organic material layer therebetween. Here, in order to increase the efficiency and stability of the organic light emitting device, the organic material layer is often composed of a multi-layered structure composed of different materials, for example, may be formed of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like. When a voltage is applied between two electrodes in the structure of the organic light emitting device, holes are injected at the anode and electrons are injected at the cathode, and excitons are formed when the injected holes meet the electrons. When it falls to the ground again, it will shine.

Conventionally, aromatic diamine derivatives and aromatic condensed ring diamine derivatives have been known as hole transport materials used in organic EL devices. However, in this case, since the applied voltage is mostly high, problems such as deterioration of device life and large power consumption have arisen. As a solution of the above problem, a method of doping an electron-accepting compound such as Lewis acid or using a hole injection layer of an organic EL device has been proposed. However, the above method has shown that there is a limitation in the hole injection and transport, and therefore, the effect of low voltage, high efficiency, and long life time can be achieved by the combination of the material between the hole transport layer or the hole control layer or the material of the hole transport layer and the multilayer hole control layer. I tried to draw. In general, the hole transport layer aromatics were substituted tertiary amines, and the device characteristics found in the combination group of the materials have shown various results. Therefore, there is a continuous demand for the development of new materials for improving device characteristics due to hole transport and carrier control.

The present specification is to provide an organic light emitting device.

This specification is the first electrode; A second electrode provided to face the first electrode; And a first organic material layer and a second organic material layer provided between the first electrode and the second electrode.

The first organic material layer includes a compound represented by Formula 1,

The second organic material layer provides an organic light emitting device comprising a compound represented by the following formula (3).

 [Formula 1]

In Formula 1,

X is O or S,

R1 to R4 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; Cyano group; Nitro group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted haloalkyl group; A substituted or unsubstituted haloalkoxy group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group, or adjacent groups combine with each other to form a substituted or unsubstituted ring,

At least one of R1 to R4 is represented by the formula (2A) or 2B,

n1 to n4 are each independently an integer of 1 to 4,

[Formula 2A]

[Formula 2B]

In Chemical Formulas 2A and 2B,

At least one of A1 to A3 is N, and the other is CH or combines with an adjacent group of L1, L2, L3, Ar4 and Ar5 to form a substituted or unsubstituted ring,

L1 to L3 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 divalent heterocyclic group, or combine with an adjacent group of A1 to A3 to form a substituted or unsubstituted ring,

Ar4 and Ar5 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group, or combine with an adjacent group of A1 to A3 to form a substituted or unsubstituted ring,

Ar6 is hydrogen; heavy hydrogen; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroring group, a is an integer from 0 to 5,

[Formula 3]

In Chemical Formula 3,

Ar1 and Ar2 each represent a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,

Ar3 is a substituted or unsubstituted divalent to tetravalent alkyl group; A substituted or unsubstituted divalent to tetravalent aryl group; Or a substituted or unsubstituted divalent to tetravalent cycloalkyl group,

At least one of X1 to X3 is N, and the rest are CH;

L is a direct bond; Or a substituted or unsubstituted arylene group,

n5 is an integer of 2 to 4,

In Formulas 1 to 3, when a and n1 to n5 are each independently 2 or more, the substituents in parentheses are the same as or different from each other.

The organic light emitting device using the compound according to the exemplary embodiment of the present specification in the hole blocking layer, the electron control layer, the electron transport layer, or the electron injection and transport layer, respectively, can have a low driving voltage, high luminous efficiency, or long life.

1, 3, and 4 show an example of an organic light emitting device in which the substrate 1, the anode 2, the light emitting layer 3, and the cathode 4 are sequentially stacked.

2, the substrate 1, the anode 2, the hole transport layer 5, the light emitting layer 3, the hole blocking layer or the electron control layer 6 electron injection and transport layer 7 and the cathode 4 are sequentially stacked It shows an example of the organic light emitting device.

[Description of codes]

1: Substrate

2: anode

3: light emitting layer

4: Cathode

5: hole transport layer

6: Hole blocking layer or electron control layer

7: electron injection and transport layer

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

In this specification, when a member is located "on" another member, this includes not only when one member is in contact with another member but also when another member exists between the two members.

In the present specification, when a part “includes” a certain component, this means that other components may be further included rather than excluding other components, unless otherwise stated.

This specification is the first electrode; A second electrode provided to face the first electrode; And a first organic material layer and a second organic material layer provided between the first electrode and the second electrode, wherein the first organic material layer includes a compound represented by Chemical Formula 1, and the second organic material layer is represented by Chemical Formula 3 It provides an organic light emitting device comprising the compound represented.

According to the exemplary embodiment of the present specification, the compound represented by Chemical Formula 1 has an advantage of controlling triplet energy by having the core structure as described above, and may exhibit long life and high efficiency.

In addition, an organic light emitting device including the compound represented by Chemical Formula 1 in the first organic material layer of the organic light emitting device, and including the compound represented by Chemical Formula 3 as the second organic material layer of the organic light emitting device has an energy relationship of the following Formula 1 Have

[Equation 1]

E _Et > E _Ec

In Formula 1, E _Et is the electron affinity of the compound represented by Formula 3 included in the second organic material layer (Electron Affinity (eV)), E _Ec is represented by Formula 1 included in the first organic material layer Electron affinity (EV) of the compound represented.

Since the compound represented by Chemical Formula 1 and the compound represented by Chemical Formula 3 exhibit the energy relationship as described above, the amount of electrons transferred from the second organic material layer containing the compound represented by Chemical Formula 3 is represented by Chemical Formula 1 The first organic material layer containing the compound may be appropriately controlled to improve the efficiency and lifetime of the organic light emitting device.

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

The term "substitution" 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 to a position where the hydrogen atom is substituted, that is, a position where the substituent can be substituted, and when two or more are substituted , 2 or more substituents may be the same or different from each other.

As used herein, the term "substituted or unsubstituted" is hydrogen; Halogen group; Nitrile group; Nitro group; Hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted amine group; A substituted or unsubstituted aryl group; And it is substituted with one or two or more substituents selected from the group consisting of a substituted or unsubstituted heterocyclic group, or two or more of the substituents exemplified above are substituted with a substituent, or means that do not have any substituents. For example, "a substituent having two or more substituents" 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 chain, carbon number is not particularly limited, but is preferably 1 to 60. 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-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, and the like.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, 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, and the like, but is not limited thereto. Does not.

In the present specification, the alkoxy group may be a straight chain, branched chain or cyclic chain. The number of carbon atoms of the alkoxy group is not particularly limited, but is preferably 1 to 20 carbon atoms. Specifically, methoxy, ethoxy, n-propoxy, isopropoxy, i-propyloxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, Isopentyloxy, n-hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, benzyloxy, p-methylbenzyloxy, etc. It may be, but is not limited to this.

In the present specification, the alkenyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1- Butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2- ( Naphthyl-1-yl) vinyl-1-yl, 2,2-bis (diphenyl-1-yl) vinyl-1-yl, steelbenyl group, styrenyl group, and the like, but are not limited thereto.

In the present specification, the amine group is selected from the group consisting of -NH ₂ , an alkylamine group, an N-alkylarylamine group, an arylamine group, an N-arylheteroarylamine group, an N-alkylheteroarylamine group, and a heteroarylamine group. Although it may be selected, the carbon number 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, and 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-phenanthre And a nilfluorenylamine group, an N-biphenyl fluorenylamine group and the like, but is 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 is preferably 6 to 25 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 preferable that it is C10-60. Specifically, the polycyclic aryl group may be naphthyl group, anthracene group, phenanthrene group, pyrene group, perylene group, chrysene group, fluorene group and the like, but is not limited thereto.

In the present specification, the fluorene group may be substituted, and adjacent substituents may combine with each other to form a ring.

등이 될 수 있으나, 이에 한정되는 것은 아니다.When the fluorene group is substituted,

And the like, but is not limited thereto.

In the present specification, the heterocyclic group includes one or more atoms other than carbon and heteroatoms, and specifically, the heteroatoms may include one or more atoms selected from the group consisting of O, N, Se, and S, and the like. Although carbon number of a heterocyclic group is not specifically limited, It is preferable that it is C2-C60. Examples of the heterocyclic group include thiophene group, furan group, pyrrole group, imidazole group, thiazole group, oxazole group, oxadiazole group, pyridine group, bipyridine group, pyrimidine group, triazine group, triazole group, acridine group , Pyridazine group, pyrazine group, quinoline group, quinazoline group, quinoxaline group, phthalazine group, pyrido pyrimidine group, pyrido pyrazine group, pyrazino pyrazine group, isoquinoline group, indole group, carbazole group, benz Oxazole group, benzimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuran group, phenanthridine group, phenanththroline group, isoxazole group, thiaxazole group Diazole group, dibenzofuran group, dibenzosilol group, phenoxathiine, phenoxazine group, phenoxazine group, phenothiazine group, dihydroindenocarbazole group, spirofluorene xanthene group and spirofluorene Thioxanthene groups, etc., but are not limited thereto. Is not. In the present specification, in the substituted or unsubstituted ring formed by bonding adjacent groups to each other, "ring" is a substituted or unsubstituted hydrocarbon ring; Or a substituted or unsubstituted hetero ring.

In the present specification, the hydrocarbon ring may be an aromatic hydrocarbon, an aliphatic hydrocarbon or a condensed ring of an aromatic hydrocarbon and an aliphatic hydrocarbon, and may be selected from examples of the cycloalkyl group or the aryl group except for the above-mentioned monovalent.

In the present specification, the aromatic hydrocarbon ring may be monocyclic or polycyclic, and may be selected from examples of the aryl group except that it is not monovalent.

In the present specification, the heterocycle is a non-carbon atom, and contains at least one heteroatom, specifically, the heteroatom may include at least one atom selected from the group consisting of O, N, Se, and S. The heterocycle may be monocyclic or polycyclic, may be aromatic, aliphatic or a condensed ring of aromatic and aliphatic, and may be selected from examples of the heterocyclic group except that it is not monovalent.

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

In the present specification, the divalent heterocyclic group refers to a divalent group having two bonding positions in the heterocyclic group. The description of the aforementioned heterocyclic groups can be applied except that they are each divalent.

In the present specification, the divalent to tetravalent alkyl group refers to those having two to four bond positions, that is, divalent to tetravalent groups. The description of the aforementioned alkyl groups can be applied except that they are each 2 to 4 valent groups.

In the present specification, the divalent to tetravalent aryl group refers to those having two to four bond positions, that is, divalent to tetravalent groups. The description of the aforementioned aryl groups can be applied except that they are each 2 to 4 valent groups.

In the present specification, the divalent to tetravalent cycloalkyl group refers to those having two to four bond positions, that is, divalent to tetravalent groups. The description of the cycloalkyl group described above can be applied except that they are each 2 to 4 valent groups.

According to an exemplary embodiment of the present specification, the R1 to R4 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; Cyano group; Nitro group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted haloalkyl group; A substituted or unsubstituted haloalkoxy group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group, or adjacent groups combine with each other to form a substituted or unsubstituted ring.

According to an exemplary embodiment of the present specification, the R1 to R4 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroring group.

According to an exemplary embodiment of the present specification, the R1 to R4 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroring group.

According to an exemplary embodiment of the present specification, the R1 to R4 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Or a substituted or unsubstituted heterocyclic group having 2 to 60 carbon atoms.

According to an exemplary embodiment of the present specification, the R1 to R4 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted aryl group having 6 to 30 carbon atoms; Or a substituted or unsubstituted heterocyclic group having 2 to 30 carbon atoms.

According to an exemplary embodiment of the present specification, the R1 to R4 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Substituted or unsubstituted aryl group having 6 to 15 carbon atoms; Or a substituted or unsubstituted heterocyclic group having 2 to 15 carbon atoms.

According to an exemplary embodiment of the present specification, a group other than the general formula 2A or 2B of the R1 to R4 is hydrogen or deuterium.

According to an exemplary embodiment of the present specification, at least one of the groups R1 to R4 other than the general formula 2A or 2B is an alkyl group, an aryl group, or an aryl group substituted with an alkyl group, the rest is hydrogen or deuterium.

According to an exemplary embodiment of the present specification, at least one of the groups R1 to R4 other than the following formula A or 2B is a methyl group; n-butyl group; tert-butyl group; A phenyl group unsubstituted or substituted with a methyl group or a tert-butyl group; Naphthyl group; Or a fluorene group substituted with a methyl group, and the remainder is hydrogen or deuterium.

According to an exemplary embodiment of the present specification, n1 is 2, and the adjacent R1 combines with each other to form a substituted or unsubstituted ring.

According to an exemplary embodiment of the present specification, n1 is 2, and the adjacent R1 combine with each other to form a substituted or unsubstituted hydrocarbon ring.

According to an exemplary embodiment of the present specification, n1 is 2, and the adjacent R1 combine with each other to form a substituted or unsubstituted aromatic hydrocarbon ring.

According to an exemplary embodiment of the present disclosure, wherein n1 is 2, the adjacent R1 is bonded to each other to form a substituted or unsubstituted benzene ring.

According to an exemplary embodiment of the present disclosure, the n1 is 2, the adjacent R1 is bonded to each other to form a benzene ring.

According to an exemplary embodiment of the present disclosure, wherein n2 is 2, the adjacent R2 combines with each other to form a substituted or unsubstituted ring.

According to an exemplary embodiment of the present specification, n2 is 2 and the adjacent R2 are bonded to each other to form a substituted or unsubstituted hydrocarbon ring.

According to an exemplary embodiment of the present disclosure, wherein n2 is 2, the adjacent R2 combines with each other to form a substituted or unsubstituted aromatic hydrocarbon ring.

According to an exemplary embodiment of the present specification, n2 is 2, and the adjacent R2 are bonded to each other to form a substituted or unsubstituted benzene ring.

According to an exemplary embodiment of the present specification, n2 is 2, and the adjacent R2 are bonded to each other to form a benzene ring.

According to an exemplary embodiment of the present specification, the n1 is 2, the adjacent R1 is bonded to each other to form a substituted or unsubstituted ring, the n2 is 2, the adjacent R2 is bonded to each other to form a benzene ring. .

According to an exemplary embodiment of the present specification, at least one of the R1 to R4 is represented by the formula 2A or 2B.

[Formula 2A]

[Formula 2B]

In Formulas 2A and 2B, the definitions of L1 to L3, Ar4 to Ar6, A1 to A3 and a are as described above.

According to an exemplary embodiment of the present specification, one of the R1 to R4 is represented by the formula 2A or 2B.

According to an exemplary embodiment of the present specification, two of the R1 to R4 are represented by the formula 2A or 2B.

According to an exemplary embodiment of the present specification, one of the R2 and one of the R3 is represented by the formula 2A or 2B.

According to an exemplary embodiment of the present disclosure, at least one of A1 to A3 is N, the remainder is CH, or combine with an adjacent group of L1, L2, L3, Ar4 and Ar5 to form a substituted or unsubstituted ring.

According to an exemplary embodiment of the present specification, the L1 to L3 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 heterocyclic group, or combine with an adjacent group of A1 to A3 to form a substituted or unsubstituted ring.

According to an exemplary embodiment of the present specification, the L1 to L3 are the same as or different from each other, and each independently a direct bond; A substituted or unsubstituted arylene group having 6 to 60 carbon atoms; Or a substituted or unsubstituted heterocyclic group having 2 to 60 carbon atoms.

According to an exemplary embodiment of the present specification, the L1 to L3 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 heterocyclic group having 2 to 30 carbon atoms.

According to an exemplary embodiment of the present specification, the L1 to L3 are the same as or different from each other, and each independently a direct bond; A substituted or unsubstituted arylene group having 6 to 15 carbon atoms; Or a substituted or unsubstituted heterocyclic group having 2 to 15 carbon atoms.

According to an exemplary embodiment of the present specification, the L1 to L3 are the same as or different from each other, and each independently a direct bond; Phenylene group; Or a biphenylylene group.

According to an exemplary embodiment of the present specification, L3 is a direct bond; Phenylene group; Biphenylylene group; Naphthylene group; Divalent thiophene group; Divalent furan group; Divalent dibenzothiophene group; Divalent dibenzofuran group; Divalent carbazole groups unsubstituted or substituted with an aryl group or an alkylaryl group; Divalent benzocarbazole groups unsubstituted or substituted with an aryl group or an alkylaryl group; Divalent dibenzosilol groups substituted or substituted with alkyl groups; Divalent phenoxathiine group; Divalent phenoxazine; Divalent phenothiazine group; Divalent pyridine group; A divalent dihydroindenocarbazole group unsubstituted or substituted with an alkyl group; Divalent groups in which dibenzothiophene and a phenyl group are linked; Or a divalent group linked to a carbazole and a phenyl group.

According to an exemplary embodiment of the present specification, L3 is a direct bond; Phenylene group; Biphenylylene group; Naphthylene group; Divalent thiophene group; Divalent furan group; Divalent dibenzothiophene group; Divalent dibenzofuran group; Divalent carbazole groups unsubstituted or substituted with a phenyl group or a methylphenyl group; Divalent benzocarbazole groups unsubstituted or substituted with a phenyl group or a methylphenyl group; Divalent dibenzosilol group substituted or substituted with a methyl group; Divalent phenoxathiine group; Divalent phenoxazine; Divalent phenothiazine group; Divalent pyridine group; A divalent dihydroindenocarbazole group unsubstituted or substituted with a methyl group; Divalent groups in which dibenzothiophene and a phenyl group are linked; Or a divalent group linked to a carbazole and a phenyl group.

According to an exemplary embodiment of the present specification, Ar4 and Ar5 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group, or combines with an adjacent group of A1 to A3 to form a substituted or unsubstituted ring.

According to an exemplary embodiment of the present specification, Ar4 and Ar5 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Or a substituted or unsubstituted heterocyclic group having 2 to 60 carbon atoms, or combined with an adjacent group among A1 to A3 to form a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 60 carbon atoms.

According to an exemplary embodiment of the present specification, Ar4 and Ar5 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted aryl group having 6 to 30 carbon atoms; Or a substituted or unsubstituted heterocyclic group having 2 to 30 carbon atoms, or combine with an adjacent group of A1 to A3 to form a substituted or unsubstituted benzene ring.

According to an exemplary embodiment of the present specification, Ar4 and Ar5 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Substituted or unsubstituted aryl group having 6 to 20 carbon atoms; Or a substituted or unsubstituted heterocyclic group having 2 to 15 carbon atoms, or combine with an adjacent group of A1 to A3 to form a substituted or unsubstituted benzene ring.

According to an exemplary embodiment of the present specification, Ar4 and Ar5 are the same as or different from each other, and each independently substituted or unsubstituted aryl group having 6 to 20 carbon atoms; Or a substituted or unsubstituted heterocyclic group having 2 to 15 carbon atoms, or combine with an adjacent group of A1 to A3 to form a substituted or unsubstituted benzene ring.

According to an exemplary embodiment of the present specification, Ar4 and Ar5 are the same as or different from each other, and each independently CN, alkyl group, alkoxy group, haloalkyl group, haloalkoxy group, alkylsilyl group, aryl group, alkylaryl group or heterocyclic ring An aryl group having 6 to 20 carbon atoms unsubstituted or substituted with a group; Or a heterocyclic group having 2 to 15 carbon atoms which is unsubstituted or substituted with a CN, an alkyl group, an alkoxy group, a haloalkyl group, a haloalkoxy group, an alkylsilyl group, an aryl group or a heterocyclic group, or is bonded to an adjacent group of A1 to A3 to benzene To form a ring.

According to an exemplary embodiment of the present specification, Ar4 and Ar5 are the same as or different from each other, and each independently a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a fluorene group, a triphenylene group, a phenanthrene group, a fluoranthene group, Phenylene group, carbazole group, benzocarbazole group, dibenzofuran group, dibenzothiophene group, dibenzosilol group, phenoxathiine group, phenoxazine group, phenoxazine group, phenothiazine group, pyridyl group, Dihydroindenocarbazole, an arylsilyl group, an alkylsilyl group, a spirofluorene xanthene group and a group in which one or two or more groups selected from spirofluorene thioxanthene groups are bonded, and these are CN, an alkyl group, an alkoxy group and a haloalkyl group. It may be substituted with a haloalkoxy group, an alkylsilyl group, an aryl group, an alkylaryl group or a heterocyclic group. Wherein the heterocyclic group as a substituent is a carbazole group, a benzocarbazole group, a dibenzofuran group, a dibenzothiophene group, a dibenzosilol group, a phenoxathiine, a phenoxazine group, a phenothiazine group, It may be a pyridyl group or a dihydroindenocarbazole group, and the aryl group as a substituent may be a phenyl group, a biphenyl group, a naphthyl group, or a triphenylene group. In addition, the alkyl group may be a methyl group, or tert-butyl group, the alkoxy group may be a methoxy group, the haloalkyl group may be a trifluoromethyl group, the haloalkoxy group may be a trifluoromethoxy group, the alkyl The silyl group may be a methylsilyl group.

In one embodiment of the present specification, Chemical Formula 1 is represented by any one of the following Chemical Formulas 1-1 to 1-5.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

In Chemical Formulas 1-1 to 1-5,

The definitions of X, R1 to R4, L1 to L3, A1 to A3, Ar4, Ar5 and n1 to n4 are the same as defined in Chemical Formulas 1 and 2A, and L1 ', L2', L3 ', A1', A2 'and A3. ', Ar4' and Ar5 'are the same as the definitions of L1, L2, L3, A1, A2, A3, Ar4 and Ar5, respectively.

In one embodiment of the present specification, two of A1 to A3 of Formula 2A are N.

In one embodiment of the present specification, A1 to A3 of Formula 2A are N.

In one embodiment of the present specification, Chemical Formula 2A may be selected from the following structural formulas.

In the above structural formula, the definitions of L1 to L3, Ar4 and Ar5 are as described above.

In one embodiment of the present specification, Ar6 of Formula 2B is hydrogen.

In one embodiment of the present specification, Ar1 and Ar2 are the same as or different from each other, and each independently a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroring group.

In one embodiment of the present specification, Ar1 and Ar2 are the same as or different from each other, and each independently a substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Or a substituted or unsubstituted heterocyclic group having 2 to 60 carbon atoms.

In one embodiment of the present specification, Ar1 and Ar2 are the same as or different from each other, and each independently a substituted or unsubstituted aryl group having 6 to 30 carbon atoms; Or a substituted or unsubstituted heterocyclic group having 2 to 30 carbon atoms.

In one embodiment of the present specification, Ar1 and Ar2 are the same as or different from each other, and each independently a substituted or unsubstituted aryl group having 6 to 15 carbon atoms; Or a substituted or unsubstituted heterocyclic group having 2 to 15 carbon atoms.

In one embodiment of the present specification, Ar1 and Ar2 are the same as or different from each other, and each independently a substituted or unsubstituted aryl group having 6 to 15 carbon atoms; Or a substituted or unsubstituted heterocyclic group having 2 to 15 carbon atoms.

In one embodiment of the present specification, Ar1 and Ar2 are the same as or different from each other, and each independently an aryl group unsubstituted or substituted with deuterium, CN, a halogen group, an alkyl group, a haloalkyl group, an alkoxy group, or an aryl group; Or a heterocyclic group.

In one embodiment of the present specification, Ar1 and Ar2 are the same as or different from each other, and each independently a phenyl group unsubstituted or substituted with deuterium, CN, a halogen group, an alkyl group, a haloalkyl group, an alkoxy group, or an aryl group; Biphenyl group; Naphthyl group; Pyridine group; Or a thiophene group.

In one embodiment of the present specification, Ar1 and Ar2 are the same as or different from each other, and are each independently substituted or unsubstituted with deuterium, CN, F, trifluoromethyl group, methyl group, tert-butyl group, methoxy group, or phenyl group Phenyl group; Biphenyl group; Naphthyl group; Pyridine group; Or a thiophene group.

In one embodiment of the present specification, n5 is 2.

In one embodiment of the present specification, n5 is 2, and the substituents in the parentheses are the same as or different from each other.

In one embodiment of the present specification, Ar3 is a substituted or unsubstituted divalent aryl group; Or a substituted or unsubstituted divalent cycloalkyl group.

In one embodiment of the present specification, Ar3 is a substituted or unsubstituted divalent aryl group having 6 to 60 carbon atoms; Or a substituted or unsubstituted divalent cycloalkyl group having 3 to 60 carbon atoms.

In one embodiment of the present specification, Ar3 is a substituted or unsubstituted divalent aryl group having 6 to 30 carbon atoms; Or a substituted or unsubstituted divalent cycloalkyl group having 3 to 30 carbon atoms.

In one embodiment of the present specification, Ar3 is a substituted or unsubstituted divalent aryl group having 6 to 15 carbon atoms; Or a substituted or unsubstituted divalent cycloalkyl group having 3 to 15 carbon atoms.

In one embodiment of the present specification, Ar3 is a substituted or unsubstituted phenylene group; A substituted or unsubstituted naphthylene group; A substituted or unsubstituted divalent phenanthrene group; Or a substituted or unsubstituted divalent cycloalkyl group.

In one embodiment of the present specification, Ar3 is a substituted or unsubstituted phenylene group; A substituted or unsubstituted naphthylene group; A substituted or unsubstituted divalent phenanthrene group; Or a substituted or unsubstituted cyclohexanylene group.

In one embodiment of the present specification, Ar3 is a phenylene group; Naphthylene group; Divalent phenanthrene group; Or a cyclohexanylene group.

In one embodiment of the present specification, Ar3 is a naphthylene group; Divalent phenanthrene group; Or a cyclohexanylene group.

In one embodiment of the present specification, Ar3 is a substituted or unsubstituted divalent tricyclic or more aryl group; Or a substituted or unsubstituted divalent cycloalkyl group.

In one embodiment of the present specification, Ar3 is a divalent tricyclic or higher aryl group; Or a divalent cycloalkyl group.

In one embodiment of the present specification, Ar3 is a divalent phenanthrene group; Or a cyclohexanylene group

In one embodiment of the present specification, Ar3 is a substituted or unsubstituted divalent alkyl group.

In one embodiment of the present specification, Ar3 is a substituted or unsubstituted divalent alkyl group having 1 to 60 carbon atoms.

In one embodiment of the present specification, Ar3 is a substituted or unsubstituted divalent alkyl group having 1 to 30 carbon atoms.

In one embodiment of the present specification, Ar3 is a substituted or unsubstituted divalent alkyl group having 1 to 15 carbon atoms.

In one embodiment of the present specification, Ar3 is a divalent alkyl group unsubstituted or substituted with an aryl group.

In one embodiment of the present specification, Ar3 is a divalent alkyl group unsubstituted or substituted with a phenyl group.

In one embodiment of the present specification, Ar3 is a methylene group unsubstituted or substituted with a phenyl group.

In one embodiment of the present specification, at least one of the X1 to X3 is N, the remainder is CH.

In one embodiment of the present specification, X1 is N and the others are CH.

In one embodiment of the present specification, X2 is N and the others are CH.

In one embodiment of the present specification, X3 is N and the others are CH.

In one embodiment of the present specification, X1 and X2 are N and the others are CH.

In one embodiment of the present specification, X1 and X3 are N and the others are CH.

In one embodiment of the present specification, X2 and X3 are N and the others are CH.

In one embodiment of the present specification, X1 to X3 are N.

In one embodiment of the present specification, L is a direct bond.

In one embodiment of the present specification, L is a substituted or unsubstituted arylene group.

In one embodiment of the present specification, L is a substituted or unsubstituted arylene group having 6 to 60 carbon atoms.

In one embodiment of the present specification, L is a substituted or unsubstituted arylene group having 6 to 30 carbon atoms.

In one embodiment of the present specification, L is a substituted or unsubstituted arylene group having 6 to 15 carbon atoms.

In one embodiment of the present specification, L is a substituted or unsubstituted phenylene group.

In one embodiment of the present specification, L is a phenylene group.

In addition, in an exemplary embodiment of the present specification, Chemical Formula 1 is selected from the following structural formulas.

In addition, in an exemplary embodiment of the present specification, Chemical Formula 3 is selected from the following structural formulas.

The first and second organic material layers of the organic light emitting device of the present specification may have a single layer structure, but may have a multi-layered structure in which two or more organic material layers are stacked. For example, the first organic material layer of the present specification may be composed of 1 to 3 layers. In addition, the organic light emitting device of the present specification may have a structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, or the like as an organic material layer or a structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron injection and transport layer, and the like. . However, the structure of the organic light emitting device is not limited thereto, and may include more or fewer organic layers.

In one embodiment of the present specification, the organic light emitting device further includes one or two or more layers selected from the group consisting of a hole injection layer, a hole transport layer, an electron injection layer, an electron blocking layer and a hole blocking layer.

In one embodiment of the present specification, the organic light emitting device further includes one or two or more layers selected from the group consisting of a hole injection layer, a hole transport layer, an electron injection and transport layer, an electron blocking layer and a hole blocking layer.

In one embodiment of the present specification, the organic light emitting device further includes one or two or more layers selected from the group consisting of a hole injection layer, a hole transport layer, an electron injection and transport layer, a hole control layer and an electron control layer.

In addition, the organic light emitting device may further include an electron charge generating layer.

In one embodiment of the present specification, the organic light emitting device includes a first electrode; A second electrode provided to face the first electrode; And at least two light emitting layers provided between the first electrode and the second electrode. Two or more first and second organic material layers provided between the two or more light emitting layers and the first electrode or between the two or more light emitting layers and the second electrode, wherein the two or more first and second organic material layers Each includes a compound represented by Chemical Formula 1 or a compound represented by Chemical Formula 3.

According to the exemplary embodiment of the present specification, the first organic material layer includes a hole blocking layer or an electron control layer, the second organic material layer includes an electron transport layer, and the hole blocking layer or the electron control layer is represented by Chemical Formula 1 To include a compound, the electron transport layer may include a compound represented by the formula (3).

According to the exemplary embodiment of the present specification, the first organic material layer includes a hole blocking layer or an electron control layer, the second organic material layer includes an electron injection and transport layer, and the hole blocking layer or the electron control layer is represented by Chemical Formula 1 It includes a compound represented by, and the electron injection and transport layer may include a compound represented by the formula (3).

In an exemplary embodiment of the present specification, the first and second organic material layers further include a hole injection layer or a hole transport layer including a compound including an arylamino group, a carbazole group or a benzocarbazole 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 in which an anode, one or more organic material layers, and a cathode are sequentially stacked on a substrate.

 In another exemplary 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 the organic light emitting device according to the exemplary embodiment of the present specification is illustrated in FIGS. 1 to 4.

4 illustrates a structure of a general organic light emitting device in which a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4 are sequentially stacked. Also, referring to FIGS. 1 and 3, the organic light emitting diode according to the exemplary embodiment of the present specification may include two or more light emitting layers. In addition, each light emitting layer may independently include a fluorescent dopant or a phosphorescent dopant. When the light emitting layer is two layers, one light emitting layer may include a fluorescent dopant, and the other light emitting dopant.

In example embodiments, the organic light emitting diode may include two or more light emitting layers emitting light of different wavelength bands between the first electrode and the second electrode.

In addition, according to the exemplary embodiment of the present specification, the two or more light emitting layers may be provided in the vertical direction of the direction of the second electrode from the first electrode, or may be provided in the horizontal direction.

2 shows a substrate 1, an anode 2, a hole transport layer 5, a light emitting layer 3, a hole blocking layer or an electron control layer 6, an electron injection and transport layer 7 and a cathode 4 sequentially. The structure of the stacked organic light emitting device is illustrated. Referring to FIG. 2, another organic light emitting diode according to an exemplary embodiment of the present specification may include three or more light emitting layers. In addition, another layer may be additionally provided between each light emitting layer and the light emitting layer. When the light emitting layer is provided with three or more layers, each light emitting layer may include a blue fluorescent light emitting layer. In addition, in the structure shown in FIG. 3, the compound represented by Chemical Formula 1 may be included in the hole blocking layer or the electron control layer 6, and the compound represented by Chemical Formula 3 may be included in the electron injection and transport layer 7.

In addition, according to the exemplary embodiment of the present specification, the light emitting layer of the three or more layers may be provided in a vertical direction of the direction of the second electrode from the first electrode, or may be provided in the horizontal direction. More specifically, the first electrode may be provided in a horizontal direction in the direction of the second electrode.

According to an exemplary embodiment of the present specification, the blue fluorescent light emitting layer includes a host and a dopant, and the host may be any one selected from the following structures.

The organic light emitting device of the present specification is a material and method known in the art, except that at least one layer of the first or second organic material layer includes a compound of the present specification, that is, the compounds represented by Chemical Formulas 1 and 3 above. Can be prepared.

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

 The organic light emitting device of the present specification is a material and method known in the art except that at least one layer of the first or second organic material layer includes the compound, that is, the compound represented by any one of Formulas 1 and 3 above. Can be prepared.

For example, the organic light emitting device of the present specification may be manufactured by sequentially stacking first electrodes, first and second organic material layers, and second electrodes on a substrate. At this time, using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation, metal or conductive metal oxides or alloys thereof are deposited on the substrate to form an anode. And, after forming a hole injection layer, a hole transport layer, an organic material layer including a light emitting layer and an electron transport layer, 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 formed by sequentially depositing a cathode material, an organic material layer, and a cathode material on a substrate.

In addition, the compounds of Formulas 1 and 3 may be formed as an organic layer by a solution coating method as well as a vacuum deposition method in the manufacture of the organic light emitting device. Here, the solution application method means spin coating, dip coating, doctor blading, inkjet printing, screen printing, spraying, roll coating, and the like, but is not limited to these.

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

In one embodiment of the present specification, 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 generally preferred to facilitate hole injection. Specific examples of the positive electrode 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); ZnO: Al or SnO ₂ : Combination of metal and oxide such as Sb; Conductive polymers such as poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDOT), polypyrrole, and polyaniline, but are not limited thereto.

It is preferable that the cathode material is a material having a small work function to facilitate electron injection. 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; Multilayer structure materials such as LiF / Al or LiO ₂ / Al, and the like, but are not limited thereto.

The hole injection material is a layer for injecting holes from an electrode, and the hole injection material has the ability to transport holes, and thus has a hole injection effect at an anode, an excellent hole injection effect for a light emitting layer or a light emitting material, and is produced in a light emitting layer A compound that prevents migration of the excited excitons to the electron injection layer or the electron injection material, and has excellent thin film formation ability is preferred. It is preferable that the highest occupied molecular orbital (HOMO) 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 the hole injection material include metal porphyrin, oligothiophene, arylamine-based organic matter, hexanitrile hexaazatriphenylene-based organic matter, quinacridone-based organic matter, and perylene-based Organic materials, anthraquinones, and 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 light emitting layer. As a hole transport material, the hole is transported to the light emitting layer by transporting holes from the anode or the hole injection layer, and the mobility of holes is large. The material is suitable. Specific examples include arylamine-based organic materials, conductive polymers, and block copolymers having a conjugated portion and a non-conjugated portion, but are not limited thereto.

As the light-emitting material, a material capable of emitting light in the visible light region by receiving and bonding holes and electrons from the hole transport layer and the electron transport layer, respectively, is preferably a material having good quantum efficiency for fluorescence or phosphorescence. 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 compounds; Poly (p-phenylenevinylene) (PPV) polymers; Spiro compounds; Polyfluorene, rubrene, and the like, but are not limited to these.

The electron transporting material is a layer that receives electrons from the electron injection layer and transports the electrons to the light emitting layer.

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

Examples of the metal complex compound include 8-hydroxyquinolinato lithium, 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) ( There are o-cresolato) gallium, bis (2-methyl-8-quinolinato) (1-naphtholato) aluminum, bis (2-methyl-8-quinolinato) (2-naphtholato) gallium, It is not limited to this.

The hole blocking layer is a layer that blocks the reaching of the cathode of the hole, and may be an electron control layer to control electrons reaching the light emitting layer. In addition, the electron charge generating layer is a layer for generating an electron charge.

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

Fabrication of the organic light emitting device including the compound represented by Chemical Formulas 1 and 3 will be described in detail in the following Examples. However, the following examples are intended to illustrate the present specification, and the scope of the present specification is not limited by them.

Preparation Example 1 Preparation of Compound EC1

The compound EC1-A (10 g, 26.6 mmol) and the compound EC1-B (12.3 g, 26.6 mmol) were completely dissolved in tetrahydrofuran (100 mL), followed by potassium carbonate (11.0 g, 79.7 mmol) in water 50 dissolved in mL and added. Tetrakistriphenyl-phosphinopalladium (0.92 g, 0.797 mmol) was added thereto, followed by heating and stirring for 8 hours. After the temperature was lowered to room temperature and the reaction was terminated, the white carbonate was filtered by removing the potassium carbonate solution. The filtered white solid was washed twice with tetrahydrofuran and ethyl acetate each to prepare compound EC1 (15.4 g, yield 81%).

MS [M + H] ⁺ = 716

Preparation Example 2 Preparation of Compound EC2

Except that each starting material was the same as the reaction scheme, the compound represented by the formula EC2 was prepared in the same manner as in the preparation method of EC1 of Preparation Example 1.

MS [M + H] ⁺ = 553

Preparation Example 3 Preparation of Compound EC3

Except that each starting material was the same as the reaction scheme, the compound represented by the formula EC3 was prepared in the same manner as the preparation method of EC1 of Preparation Example 1.

MS [M + H] ⁺ = 640

Preparation Example 4 Preparation of Compound EC4

Except that each starting material was the same as the reaction scheme, the compound represented by the formula EC4 was prepared by the same method as the preparation method of EC1 of Preparation Example 1.

MS [M + H] ⁺ = 640

Preparation Example 5 Preparation of Compound EC5

The compound EC5-A (10 g, 17.1 mmol) and the compound EC5-B (9.2 g, 34.2 mmol) were completely dissolved in tetrahydrofuran (100 mL), followed by potassium carbonate (7.1 g, 51.3 mmol) in water 50 dissolved in mL and added. Tetrakistriphenyl-phosphinopalladium (0.59 g, 0.513 mmol) was added thereto, followed by heating and stirring for 8 hours. After the temperature was lowered to room temperature and the reaction was terminated, the white carbonate was filtered by removing the potassium carbonate solution. The filtered white solid was washed twice with tetrahydrofuran and ethyl acetate to prepare compound EC5 (9.5 g, yield 70%).

MS [M + H] ⁺ = 795

Preparation Example 6 Preparation of Compound EC6

Except that each starting material was the same as the reaction scheme, a compound represented by the formula EC6 was prepared by the same method as the preparation method of EC1 of Preparation Example 1.

MS [M + H] ⁺ = 807

Preparation Example 7 Preparation of Compound EC7

A compound represented by Chemical Formula EC7 was prepared by the same method as the preparation method of EC1 of Preparation Example 1, except that each starting material was performed in the same manner as in the above scheme.

MS [M + H] ⁺ = 654

Preparation Example 8 Preparation of Compound EC8

Except that each starting material was the same as the reaction scheme, a compound represented by the formula EC8 was prepared in the same manner as in the preparation method of EC1 of Preparation Example 1.

MS [M + H] ⁺ = 821

Preparation Example 9 Preparation of Compound EC9

Except that each starting material was the same as the reaction scheme, the compound represented by the formula EC9 was prepared in the same manner as in the preparation method of EC1 of Preparation Example 1.

MS [M + H] ⁺ = 848

Preparation Example 10 Preparation of Compound EC10

A compound represented by Chemical Formula EC10 was prepared by the same method as the preparation method of EC1 of Preparation Example 1, except that each starting material was performed in the same manner as in the above scheme.

MS [M + H] ⁺ = 537

Preparation Example 11 Preparation of Compound ET1

Except that each starting material was the same as the reaction scheme, the compound represented by the formula ET1 was prepared by the same method as the preparation method of EC5 of Preparation Example 1.

MS [M + H] ⁺ = 799

Preparation Example 12 Preparation of Compound ET2

Except that each starting material was the same as the reaction scheme, a compound represented by the formula ET2 was prepared by the same method as the preparation method of EC5 of Preparation Example 1.

MS [M + H] ⁺ = 743

Preparation Example 13 Preparation of Compound ET3

Except that each starting material was the same as the reaction scheme, the compound represented by the formula ET3 was prepared by the same method as the preparation method of EC5 of Preparation Example 1.

MS [M + H] ⁺ = 763

Preparation Example 14 Preparation of Compound ET4

Except that each starting material was the same as the reaction scheme, a compound represented by the formula ET4 was prepared by the same method as the preparation method of EC5 of Preparation Example 1.

MS [M + H] ⁺ = 591

Preparation Example 15 Preparation of Compound ET5

Except that each starting material was the same as the reaction scheme, a compound represented by the formula ET5 was prepared by the same method as the preparation method of EC5 of Preparation Example 1.

MS [M + H] ⁺ = 791

Preparation Example 16 Preparation of Compound ET6

Except that each starting material was the same as the reaction scheme, a compound represented by the formula ET6 was prepared by the same method as the preparation method of EC5 of Preparation Example 1.

MS [M + H] ⁺ = 759

Preparation Example 17 Preparation of Compound ET7

Except that each starting material was the same as the reaction scheme, a compound represented by the formula ET7 was prepared by the same method as the preparation method of EC5 of Preparation Example 1.

MS [M + H] ⁺ = 699

Example 1-1

A glass substrate coated with a thin film of ITO (indium tin oxide) at a thickness of 1000 에 was placed in distilled water in which detergent was dissolved and ultrasonically cleaned. In this case, Fischer Co. product was used as the detergent, and distilled water was filtered secondly as a filter of Millipore Co. product. After washing ITO for 30 minutes, ultrasonic washing was repeated 10 times with distilled water twice. After washing with distilled water, ultrasonic cleaning was performed with a solvent of isopropyl alcohol, acetone, and methanol, followed by drying and then transported to a plasma cleaner. In addition, the substrate was cleaned for 5 minutes using an oxygen plasma, and then the substrate was transferred to a vacuum evaporator.

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

Subsequently, the BH compound and the following BD compound were vacuum-deposited at a weight ratio of 25: 1 on the hole transport layer to form a light emitting layer to form a film thickness of 200 Pa.

The compound EC1 was vacuum-deposited on the emission layer to form a hole blocking layer having a thickness of 50 kHz. The compound ET1 and the following LiQ compound were vacuum deposited on the hole blocking layer in a weight ratio of 1: 1 to form an electron injection and transport layer at a thickness of 300 kPa. The cathode was formed by sequentially depositing lithium fluoride (LiF) and aluminum at a thickness of 1000 상 에 on the electron injection and transport layer sequentially.

In the above process, the deposition rate of the organic material was maintained at 0.4 to 0.9 Å / sec, the lithium fluoride of the cathode was maintained at a deposition rate of 0.3 Å / sec, and the aluminum was 2 Å / sec. ^An organic light-emitting device was manufactured by maintaining ⁻⁷ to 5 × 10 ⁻⁵ torr.

Examples 1-2 to 1-18 and Comparative Examples 1-1 to 1-18

An organic light emitting diode was manufactured according to the same method as Example 1-1 except for using the compound of Table 1 instead of the compound EC1 and ET1 of Example 1-1.

The driving voltage and the luminous efficiency of the organic light emitting diodes manufactured in Examples 1-1 to 1-18 and Comparative Examples 1-1 to 1-18 were measured at a current density of 10 mA / cm ² , and 20 mA / cm ^The time T90 of 90% of the initial luminance at the current density of ² was measured. The results are shown in Table 1 below.

Classification (Compound) Voltage (V @ 10 mA / cm ² ) Efficiency (cd / A @ 10 mA / cm ² ) Color coordinate (x, y) Lifetime (h) (T90 at 20 mA / cm ² ) Example 1-1 EC1 ET1 4.05 5.86 (0.135, 0.088) 300 Example 1-2 EC2 ET1 4.01 5.98 (0.135, 0.089) 284 Example 1-3 EC3 ET1 4.02 5.73 (0.135, 0.087) 311 Example 1-4 EC4 ET1 4.03 5.90 (0.133, 0.088) 285 Example 1-5 EC5 ET1 4.15 5.61 (0.135, 0.089) 321 Example 1-6 EC6 ET2 4.00 5.77 (0.135, 0.087) 294 Example 1-7 EC7 ET2 3.96 6.03 (0.135, 0.088) 271 Example 1-8 EC8 ET2 3.99 5.73 (0.133, 0.088) 297 Example 1-9 EC9 ET2 3.95 5.90 (0.135, 0.089) 286 Example 1-10 EC10 ET2 4.06 5.79 (0.135, 0.087) 274 Example 1-11 EC1 ET3 3.93 6.00 (0.135, 0.088) 269 Example 1-12 EC2 ET3 3.91 6.06 (0.133, 0.088) 251 Example 1-11 EC3 ET5 4.01 5.88 (0.135, 0.088) 300 Example 1-12 EC4 ET5 4.00 5.99 (0.133, 0.088) 277 Example 1-13 EC5 ET4 4.20 5.58 (0.135, 0.089) 351 Example 1-14 EC6 ET4 4.10 5.68 (0.135, 0.087) 309 Example 1-15 EC7 ET6 3.94 6.05 (0.135, 0.088) 268 Example 1-16 EC8 ET6 3.96 5.76 (0.133, 0.088) 290 Examples 1-17 EC9 ET7 3.92 5.92 (0.135, 0.089) 280 Example 1-18 EC10 ET7 4.01 5.82 (0.135, 0.087) 272 Comparative Example 1-1 EC1 ET-B 4.05 5.56 (0.135, 0.088) 50 Comparative Example 1-2 EC2 ET-B 4.01 5.48 (0.135, 0.089) 44 Comparative Example 1-3 EC3 ET-B 4.02 5.33 (0.135, 0.087) 51 Comparative Example 1-4 EC4 ET-B 4.03 5.41 (0.133, 0.088) 45 Comparative Example 1-5 EC5 ET-B 4.15 5.22 (0.135, 0.089) 61 Comparative Example 1-6 EC6 ET-B 4.00 5.36 (0.135, 0.087) 64 Comparative Example 1-7 EC7 ET-B 3.96 5.62 (0.135, 0.088) 71 Comparative Example 1-8 EC8 ET-B 3.99 5.30 (0.133, 0.088) 67 Comparative Example 1-9 EC9 ET-B 3.95 5.52 (0.135, 0.089) 66 Comparative Example 1-10 EC10 ET-B 4.06 5.40 (0.135, 0.087) 54 Comparative Example 1-11 ET-A ET1 4.35 4.06 (0.135, 0.088) 201 Comparative Example 1-12 ET-A ET2 4.26 4.53 (0.135, 0.088) 174 Comparative Example 1-13 ET-A ET3 4.22 4.46 (0.133, 0.088) 153 Comparative Example 1-14 ET-A ET4 4.42 3.28 (0.135, 0.089) 256 Comparative Example 1-15 ET-A ET5 4.51 4.68 (0.135, 0.088) 202 Comparative Example 1-16 ET-A ET6 4.34 4.65 (0.135, 0.088) 178 Comparative Example 1-17 ET-A ET7 4.31 4.72 (0.135, 0.087) 182 Comparative Example 1-18 ET-A ET-B 4.46 4.00 (0.133, 0.088) 54

Comparing Examples 1-1 to 1-18 and Comparative Examples 1-1 to 1-18 in Table 1, the organic light emitting device to which Formulas 1 and 3 according to the present specification is applied is applied to Formula 1 or Formula 3 only. It is remarkably excellent in lifespan compared with an organic light emitting element.

Example 2-1

A glass substrate coated with a thin film of ITO (indium tin oxide) at a thickness of 1000 에 was placed in distilled water in which detergent was dissolved and ultrasonically cleaned. In this case, Fischer Co. product was used as the detergent, and distilled water was filtered secondly as a filter of Millipore Co. product. After washing ITO for 30 minutes, ultrasonic washing was repeated 10 times with distilled water twice. After washing with distilled water, ultrasonic cleaning was performed with a solvent of isopropyl alcohol, acetone, and methanol, followed by drying and then transported to a plasma cleaner. In addition, the substrate was cleaned for 5 minutes using an oxygen plasma, and then the substrate was transferred to a vacuum evaporator.

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

Subsequently, a BH compound and a BD compound were vacuum deposited on the first hole transport layer at a film thickness of 200 Pa at a weight ratio of 25: 1 to form a first light emitting layer.

The compound EC1 was vacuum-deposited on the first emission layer to form a first hole blocking layer having a thickness of 50 μs. The compound ET1 and the following LiQ compound were vacuum deposited on the first hole blocking layer in a weight ratio of 1: 1 to form a first electron injection and transport layer at a thickness of 200 μs.

Compound ET-C and a lithium compound were vacuum deposited on the first electron injection and transport layer at a film thickness of 100 Pa to form an electron charge generating layer. On the electron charge generating layer, a HI-A compound was thermally vacuum-deposited to a thickness of 100 Pa to form a second hole injection layer.

The second HAT compound 50 μs and the following HT-A compound 60 μs were sequentially vacuum deposited on the second hole injection layer to form a second hole transport layer.

Subsequently, a BH compound and a BD compound were vacuum deposited on the second hole transport layer at a film thickness of 200 Pa at a weight ratio of 25: 1 to form a second light emitting layer.

Compound EC1 was vacuum deposited on the second light emitting layer to form a hole blocking layer having a thickness of 50 kHz. The compound ET1 and the following LiQ compound were vacuum deposited on the second hole blocking layer at a weight ratio of 1: 1 to form a second electron injection and transport layer at a thickness of 200 μs. A cathode was formed by sequentially depositing lithium fluoride (LiF) and aluminum at a thickness of 1000 로 on the second electron injection and transport layer sequentially.

In the above process, the deposition rate of the organic material was maintained at 0.4 to 0.9 Å / sec, the lithium fluoride of the cathode was maintained at a deposition rate of 0.3 Å / sec, and the aluminum was 2 Å / sec. ^An organic light-emitting device was manufactured by maintaining ⁻⁷ to 5 × 10 ⁻⁵ torr.

Examples 2-2 to 2-18 and Comparative Examples 2-1 to 2-18

An organic light emitting diode was manufactured according to the same method as Example 2-1 except for using the compound of Table 1 instead of the compound EC1 and ET1 of Example 2-1.

The driving voltage and the luminous efficiency of the organic light emitting diodes manufactured in Examples 2-2 to 2-18 and Comparative Examples 2-1 to 2-18 were measured at a current density of 10 mA / cm ² , and 20 mA / cm ^2. The time T90 of 90% of the initial luminance at the current density of was measured. The results are shown in Table 2 below.

Classification (Compound) Voltage (V @ 10 mA / cm ² ) Efficiency (cd / A @ 10 mA / cm ² ) Color coordinate (x, y) Lifetime (h) (T90 at 20 mA / cm ² ) Example 2-1 EC1 ET1 8.04 13.48 (0.137, 0.124) 231 Example 2-2 EC2 ET1 8.00 13.75 (0.137, 0.124) 219 Example 2-3 EC3 ET1 8.01 13.18 (0.137, 0.123) 239 Example 2-4 EC4 ET1 8.02 13.57 (0.137, 0.125) 219 Example 2-5 EC5 ET1 8.14 12.90 (0.137, 0.124) 247 Example 2-6 EC6 ET2 8.00 13.27 (0.137, 0.124) 226 Example 2-7 EC7 ET2 7.95 13.87 (0.137, 0.123) 209 Example 2-8 EC8 ET2 7.98 13.18 (0.137, 0.125) 229 Example 2-9 EC9 ET2 7.94 13.57 (0.137, 0.124) 220 Example 2-10 EC10 ET2 8.04 13.32 (0.137, 0.124) 211 Example 2-11 EC1 ET3 7.92 13.80 (0.137, 0.123) 207 Example 2-12 EC2 ET3 7.90 13.94 (0.137, 0.125) 193 Example 2-11 EC3 ET5 8.00 13.52 (0.137, 0.124) 231 Example 2-12 EC4 ET5 8.01 13.78 (0.137, 0.124) 213 Example 2-13 EC5 ET4 8.21 12.83 (0.137, 0.123) 270 Example 2-14 EC6 ET4 8.08 13.06 (0.137, 0.125) 238 Example 2-15 EC7 ET6 7.92 13.92 (0.137, 0.124) 206 Example 2-16 EC8 ET6 7.94 13.25 (0.137, 0.124) 223 Example 2-17 EC9 ET7 7.92 13.62 (0.137, 0.123) 216 Example 2-18 EC10 ET7 8.03 13.39 (0.137, 0.124) 209 Comparative Example 2-1 EC1 ET-B 8.02 12.79 (0.137, 0.124) 39 Comparative Example 2-2 EC2 ET-B 8.01 12.60 (0.137, 0.124) 34 Comparative Example 2-3 EC3 ET-B 8.01 12.26 (0.137, 0.124) 39 Comparative Example 2-4 EC4 ET-B 8.02 12.44 (0.137, 0.125) 35 Comparative Example 2-5 EC5 ET-B 8.12 12.01 (0.137, 0.124) 47 Comparative Example 2-6 EC6 ET-B 8.01 12.33 (0.137, 0.124) 49 Comparative Example 2-7 EC7 ET-B 7.94 12.93 (0.137, 0.124) 55 Comparative Example 2-8 EC8 ET-B 7.96 12.19 (0.137, 0.125) 52 Comparative Example 2-9 EC9 ET-B 7.94 12.70 (0.137, 0.124) 51 Comparative Example 2-10 EC10 ET-B 8.04 12.42 (0.137, 0.124) 42 Comparative Example 2-11 ET-A ET1 8.35 9.34 (0.137, 0.123) 155 Comparative Example 2-12 ET-A ET2 8.26 10.42 (0.137, 0.123) 134 Comparative Example 2-13 ET-A ET3 8.22 10.26 (0.137, 0.124) 118 Comparative Example 2-14 ET-A ET4 8.42 7.54 (0.137, 0.124) 197 Comparative Example 2-15 ET-A ET5 8.51 10.76 (0.137, 0.123) 156 Comparative Example 2-16 ET-A ET6 8.34 10.70 (0.137, 0.125) 137 Comparative Example 2-17 ET-A ET7 8.31 10.86 (0.137, 0.124) 140 Comparative Example 2-18 ET-A ET-B 8.46 9.2 (0.137, 0.124) 42

When comparing Examples 2-1 to 2-18 and Comparative Examples 2-1 to 2-18 in Table 2, the organic light emitting device to which the formula 1 and formula 3 according to the present specification is applied, only the formula 1 or 3 It is remarkably excellent in lifespan compared with an organic light emitting element.

Example 3

Compounds EC1 to EC10, ET1 to ET7, and ET-A to ET-B Electron Affinity (eV) values according to one embodiment of the present specification are shown in Table 3 below.

compound Electron Affinity (eV) EC1 1.38 EC2 1.26 EC3 1.42 EC4 1.32 EC5 1.67 EC6 1.60 EC7 1.36 EC8 1.38 EC9 1.56 EC10 1.17 ET1 1.85 ET2 1.7 ET3 1.53 ET4 1.69 ET5 1.55 ET6 1.74 ET7 1.68 ET-A 1.45 ET-B 1.41

Electron Affinity (eV) was performed using Gaussian 03, a quantum chemistry calculation program manufactured by Gaussian, USA, using density functional theory (DFT), B3LYP, basis function The calculated value was calculated by time dependent density functional theory (TD-DFT) for the structure optimized by using 6-31G * as an electron injection and the compound of Formula 1 used in the hole blocking layer of Table 3 The amount of electrons transferred from Formula 3, which is an electron injection and transport compound, in the organic light emitting device having the relationship of E _Et > E _Ec in the relationship of Electron Affinity (eV) with the compound of Formula 3 used in the transport layer Formula 1, which is a hole blocking layer (or electron control layer) compound, is appropriately controlled to improve efficiency and lifespan of the organic light emitting device.

Claims (13)

A first electrode; A second electrode provided to face the first electrode; And a first organic material layer and a second organic material layer provided between the first electrode and the second electrode. The first organic material layer includes a compound represented by Formula 1, The second organic material layer is an organic light emitting device comprising a compound represented by the following formula (3):  [Formula 1]

In Formula 1, X is O or S, R1 to R4 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; Cyano group; Nitro group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted haloalkyl group; A substituted or unsubstituted haloalkoxy group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group, or adjacent groups combine with each other to form a substituted or unsubstituted ring, At least one of R1 to R4 is represented by the formula (2A) or 2B, n1 to n4 are each independently an integer of 1 to 4, [Formula 2A]

[Formula 2B]

In Chemical Formulas 2A and 2B, At least one of A1 to A3 is N, and the other is CH or combines with an adjacent group of L1, L2, L3, Ar4 and Ar5 to form a substituted or unsubstituted ring, L1 to L3 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 divalent heterocyclic group, or combine with an adjacent group of A1 to A3 to form a substituted or unsubstituted ring, Ar4 and Ar5 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group, or combine with an adjacent group of A1 to A3 to form a substituted or unsubstituted ring, Ar6 is hydrogen; heavy hydrogen; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroring group, a is an integer from 0 to 5, [Formula 3]

In Chemical Formula 3, Ar1 and Ar2 each represent a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group, Ar3 is a substituted or unsubstituted divalent to tetravalent alkyl group; A substituted or unsubstituted divalent to tetravalent aryl group; Or a substituted or unsubstituted divalent to tetravalent cycloalkyl group, At least one of X1 to X3 is N, and the rest are CH; L is a direct bond; Or a substituted or unsubstituted arylene group, n5 is an integer of 2 to 4, In Formulas 1 to 3, when a and n1 to n5 are each independently 2 or more, the substituents in parentheses are the same as or different from each other. The method according to claim 1, The formula 1 is an organic light emitting device that is represented by any one of the following formula 1-1 to formula 1-5: [Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

In Chemical Formulas 1-1 to 1-5, The definitions of X, R1 to R4, L1 to L3, A1 to A3, Ar4, Ar5 and n1 to n4 are as in claim 1, and L1 ', L2', L3 ', A1', A2 ', A3', Ar4 ' And Ar5 'are as defined for L1, L2, L3, A1, A2, A3, Ar4, and Ar5, respectively. The method according to claim 1, Ar3 is a substituted or unsubstituted phenylene group; A substituted or unsubstituted naphthylene group; A substituted or unsubstituted divalent phenanthrene group; Or a substituted or unsubstituted divalent cycloalkyl group. The method according to claim 1, Formula 1 is an organic light emitting device is selected from the following structural formula:

The method according to claim 1, Formula 3 is an organic light emitting device is selected from the following structural formula:

The method according to claim 1, The compound represented by Chemical Formula 1 and the compound represented by Chemical Formula 3 are organic light emitting devices satisfying the following Equation 1: [Equation 1] E _Et > E _Ec In the formula 1, E _Et is the electron affinity (Electron Affinity (eV)) of the compound represented by the formula (3), E _Ec is the electron affinity (Electron Affinity (eV)) of the compound represented by the formula (1). The method according to claim 1, The first organic material layer is an organic light emitting device that is a hole blocking layer or an electron control layer. The method according to claim 1, The second organic material layer is an organic light emitting device that is an electron transport layer or an electron injection and transport layer. The method according to claim 1, And two or more light emitting layers emitting light of different wavelengths between the first electrode and the second electrode. The method according to claim 1, And at least two light-emitting layers between the first electrode and the second electrode, Each light emitting layer is independently, an organic light emitting device comprising a fluorescent dopant or a phosphorescent dopant. The method according to claim 1, And at least two light-emitting layers between the first electrode and the second electrode, Any one of the light emitting layer comprises a fluorescent dopant, the other light emitting layer is an organic light-emitting device comprising a phosphorescent dopant. The method according to claim 1, And at least three light-emitting layers between the first electrode and the second electrode, Each light emitting layer is an organic light emitting device that includes a blue fluorescent light emitting layer. The method according to claim 12, The three or more light-emitting layers are provided in order from the first electrode to the second electrode.

Images