KR102209929B1 - Organic light emitting device - Google Patents

Abstract

The present specification is a first electrode; A second electrode provided opposite to the first electrode; And a light emitting layer provided between the first electrode and the second electrode and including a compound of Formula 1 and a compound of Formula 2.

Description

Organic light emitting device {ORGANIC LIGHT EMITTING DEVICE}

This application claims the benefit of the filing date of the Korean patent application 10-2018-0066868 filed with the Korean Intellectual Property Office on June 11, 2018, the entire contents of which are incorporated herein.

The present specification relates to an organic light emitting device.

In general, the organic light emission phenomenon refers to a phenomenon in which electrical energy is converted into light energy using an organic material. An organic light emitting device using the organic light emitting phenomenon has a structure including an anode, a cathode, and an organic material layer therebetween. Here, the organic material layer has a multilayer structure made of different materials in order to increase the efficiency and stability of the organic light emitting device, and may include, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like. In the structure of such an organic light emitting device, when a voltage is applied between the two electrodes, holes are injected from the anode and electrons from the cathode are injected into the organic material layer, and excitons are formed when the injected holes and electrons meet. It glows when it falls to the ground.

Development of a new material for the organic light emitting device as described above is continuously required.

Korean Patent Application Publication No. 10-2007-0091540

The present specification provides an organic light emitting device.

An exemplary embodiment of the present specification is a first electrode; A second electrode provided opposite to the first electrode; And an emission layer provided between the first electrode and the second electrode and including a compound represented by Formula 1 below and a compound represented by Formula 2 below.

[Formula 1]

In Formula 1,

L1 is a direct bond; Arylene group; Or a heteroarylene group,

R1 to R3 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; Cyano group; Alkyl group; Cycloalkyl group; Alkenyl group; Alkoxy group; Aryloxy group; Amine group; Aryl group; Or a heteroaryl group,

Ar1 is an aryl group; Or a heteroaryl group unsubstituted or substituted with an aryl group,

r1 is an integer from 0 to 7,

r2 is an integer from 0 to 8,

r3 is an integer from 0 to 4,

When each of the r1 to r3 is 2 or more, the structures in the two or more parentheses are the same as or different from each other,

[Formula 2]

In Formula 2,

X is B, P(=O) or P(=S),

A1 to A3 are the same as or different from each other, and each independently a monocyclic or polycyclic ring,

G1 to G3 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Alkyl group; Aryl group; Heteroaryl group; Alkylamine group; A substituted or unsubstituted arylamine group; Or a heteroarylamine group, or may form a ring through Y3 by bonding with an adjacent group,

Y3 is a direct bond; O; C(Rm)(Rn); N(Rp); Or a substituted or unsubstituted silyl group,

Y1 and Y2 are the same as or different from each other, and each independently O or N(Rp),

Rm, Rn and Rp are the same as or different from each other, and each independently hydrogen, deuterium, an alkyl group, or a substituted or unsubstituted aryl group, or combine with an adjacent group to form a substituted or unsubstituted ring,

b1 to b3 are each an integer of 0 or more,

When b1 to b3 are each 2 or more, the structures in the two or more parentheses are the same or different from each other.

The organic light-emitting device according to the exemplary embodiment of the present specification has high luminous efficiency, excellent color reproducibility, and has a long lifespan.

1 and 2 illustrate an organic light emitting device according to an exemplary embodiment of the present specification.

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

An exemplary embodiment of the present specification is a first electrode; A second electrode provided opposite to the first electrode; And an emission layer provided between the first electrode and the second electrode and including the compound represented by Formula 1 and the compound represented by Formula 2. It provides an organic light emitting diode.

According to an exemplary embodiment of the present specification, in the compound represented by Formula 1, a substituted or unsubstituted dibenzofuran is bonded to the 9 position of anthracene through the linking group L1, and the phenylene group is the linking group at the 10th position. , Ar1 is bonded to the ortho (oroso) position where the anthracene group of the phenylene group is bonded. The structure of Chemical Formula 1 facilitates the flow of electrons and increases steric hindrance, reducing the phenomenon that each molecule is accumulated too close, so that the structure of the thin film is stable, so the organic light emitting device including this in the emission layer has a long lifespan. Has the effect of.

According to an exemplary embodiment of the present specification, the compound represented by Formula 2 includes a ring of A1 to A3 around X, and a ring is formed rigidly through Y1 and Y2 to transfer electrons to X, which lacks electrons. Thus, it has a stabilized form. In addition, the compound represented by Chemical Formula 2 has a narrow half-width of an emission spectrum, and an organic light-emitting device including the same in the emission layer has high luminous efficiency and excellent color reproducibility.

Since the organic light-emitting device according to the exemplary embodiment of the present specification uses Formula 1 having a long life effect as the emission layer and Formula 2 having excellent luminous efficiency and color reproducibility, the organic light-emitting device has a long life effect and luminous efficiency and color. There is an effect of excellent reproducibility.

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 otherwise stated.

In the present specification, when a member is said to be located "on" another member, this includes not only the case where the member is in contact with the other member, but also the case where another member exists between the two members.

Examples of the substituents 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; Cyano group; Alkyl group; Cycloalkyl group; Alkenyl group; Alkoxy group; Aryloxy group; Amine group; Aryl group; And it is substituted with one or more substituents selected from the group consisting of a heteroaryl group, two or more of the above-exemplified substituents 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 a linear or branched chain, and the number of carbon atoms is not particularly limited, but is preferably 1 to 30. 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, 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 alkenyl group may be a linear or branched chain, and the number of carbon atoms is not particularly limited, but is preferably 2 to 30. 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, stilbenyl group, styrenyl group, and the like, but are not limited thereto.

In the present specification, the alkoxy group may be linear, branched or cyclic. The number of carbon atoms of the alkoxy group is not particularly limited, but it is preferably 1 to 30 carbon atoms. Specifically, methoxy, ethoxy, n-propoxy, isopropoxy, 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., but It is not limited.

In the present specification, the aryl group is not particularly limited, but preferably has 6 to 30 carbon atoms, and the aryl group may be monocyclic or polycyclic.

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 preferable that it has 10 to 30 carbon atoms. Specifically, the polycyclic aryl group may be a naphthyl group, an anthracene group, a phenanthrene group, a triphenylene group, a pyrene group, a phenalene group, a perylene group, a chrysene group, a fluorene group, and the like, but is not limited thereto.

In the present specification, the fluorenyl group may be substituted, and adjacent groups may be bonded to each other to form a ring.

,

,

,

,

,

,

및

등이 있으나, 이에 한정되지 않는다.When the fluorenyl group is substituted,

,

,

,

,

,

,

And

And the like, but are not limited thereto.

In the present specification, the "adjacent" group means a substituent substituted on an atom directly connected to the atom where the corresponding substituent is substituted, a substituent positioned three-dimensionally closest to the corresponding substituent, or another substituent substituted on the atom where the corresponding substituent is substituted. I can. For example, two substituents substituted at an ortho position in a benzene ring and two substituents substituted at the same carbon in an aliphatic ring may be interpreted as "adjacent" groups to each other.

In the present specification, the heteroaryl group includes one or more atoms and heteroatoms other than carbon, and specifically, the heteroatom may include one or more atoms selected from the group consisting of O, N, Se, and S. The number of carbon atoms is not particularly limited, but is preferably 2 to 30 carbon atoms, and the heteroaryl group may be monocyclic or polycyclic. Examples of the heterocyclic group include a thiophene group, a furan group, a pyrrole group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a pyridine group, a bipyridine group, a pyrimidine group, a triazine group, a triazole group, an acridine group , Pyridazine group, pyrazine group, quinoline group, quinazoline group, quinoxaline group, phthalazine group, pyrido pyrimidine group, pyrido pyrazine group, pyrazino pyrazin group, isoquinoline group, indole group, carbazole group, benz Oxazole group, benzimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuran group, phenanthridine group (phenanthridine), phenanthroline group (phenanthroline), isoxazole group, thia Diazole group, phenothiazine group, dibenzofuran group, and the like, but are not limited thereto.

In the present specification, the aryl group in the aryloxy group is the same as the example of the aryl group described above. Specifically, the aryloxy group includes a phenoxy group, p-tolyloxy group, m-tolyloxy group, 3,5-dimethyl-phenoxy group, 2,4,6-trimethylphenoxy group, p-tert-butylphenoxy group, 3- Biphenyloxy group, 4-biphenyloxy group, 1-naphthyloxy group, 2-naphthyloxy group, 4-methyl-1-naphthyloxy group, 5-methyl-2-naphthyloxy group, 1-anthryloxy group , 2-anthryloxy group, 9-anthryloxy group, 1-phenanthryloxy group, 3-phenanthryloxy group, and 9-phenanthryloxy group, but are not limited thereto.

In the present specification, the amine group is 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 It may be selected, 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-phenanthre Nilfluorenylamine group, N-biphenylfluorenylamine group, and the like, but are not limited thereto.

In the present specification, the N-alkylarylamine group refers to an amine group in which an alkyl group and an aryl group are substituted with N of the amine group. The alkyl group and aryl group in the N-alkylarylamine group are the same as those of the aforementioned alkyl group and aryl group.

In the present specification, the N-arylheteroarylamine group refers to an amine group in which an aryl group and a heteroaryl group are substituted with N of the amine group. The aryl group and heteroaryl group in the N-arylheteroarylamine group are the same as the examples of the aryl group and heteroaryl group described above.

In the present specification, the N-alkylheteroarylamine group means an amine group in which an alkyl group and a heteroaryl group are substituted with N of the amine group. The alkyl group and heteroaryl group in the N-alkylheteroarylamine group are the same as those of the aforementioned alkyl group and heteroaryl group.

In the present specification, examples of the alkylamine group include a substituted or unsubstituted monoalkylamine group, or a substituted or unsubstituted dialkylamine group. The alkyl group in the alkylamine group may be a linear or branched alkyl group. The alkylamine group containing two or more alkyl groups may include a straight-chain alkyl group, a branched-chain alkyl group, or a straight-chain alkyl group and a branched-chain alkyl group at the same time. For example, the alkyl group in the alkylamine group may be selected from the examples of the alkyl group described above.

In the present specification, examples of the heteroarylamine group include a substituted or unsubstituted monoheteroarylamine group, or a substituted or unsubstituted diheteroarylamine group. The heteroarylamine group including two or more heteroaryl groups may include a monocyclic heteroaryl group, a polycyclic heteroaryl group, or a monocyclic heteroaryl group and a polycyclic heteroaryl group at the same time. For example, the heteroaryl group in the heteroarylamine group may be selected from the examples of the heteroaryl group described above.

In the present specification, an alkylaryl group means an aryl group in which an alkyl group is substituted with an aryl group. The alkyl group and the aryl group of the alkylaryl group are the same as those of the aforementioned alkyl group and aryl group.

In the present specification, in the "ring" or "a substituted or unsubstituted ring formed by bonding of adjacent groups to each other", the "ring" is a substituted or unsubstituted hydrocarbon ring; Or it means a substituted or unsubstituted heterocycle.

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

In the present specification, the aromatic 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 includes one or more atoms and heteroatoms other than carbon, and specifically, the heterocycle may include one or more atoms selected from the group consisting of O, N, Se, and S. The heterocycle may be monocyclic or polycyclic, and may be an aromatic, aliphatic, or condensed ring of aromatic and aliphatic, and may be selected from examples of the heteroaryl group or heterocyclic group except that it is not monovalent.

는 상기 화학식 1에 연결되는 부위를 의미한다.In this specification,

Means a moiety connected to Formula 1.

According to an exemplary embodiment of the present specification, Chemical Formula 1 is represented by any one of Chemical Formulas 1-1 to 1-4 below.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

In Formulas 1-1 to 1-4,

The definitions of L1, Ar1, R1 to R3, and r1 to r3 are the same as those defined in Chemical Formula 1.

According to an exemplary embodiment of the present specification, in Formula 1, L1 is a direct bond; Or a monocyclic or polycyclic arylene group having 6 to 30 carbon atoms.

According to an exemplary embodiment of the present specification, in Formula 1, L1 is a direct bond; Or a monocyclic or polycyclic arylene group having 6 to 20 carbon atoms.

According to an exemplary embodiment of the present specification, in Formula 1, L1 is a direct bond; Or a monocyclic or polycyclic arylene group having 6 to 10 carbon atoms.

According to an exemplary embodiment of the present specification, in Formula 1, L1 is a direct bond; Phenylene group; Or it is a naphthylene group.

According to an exemplary embodiment of the present specification, in Formula 1, R1 is hydrogen; Or a monocyclic or polycyclic aryl group having 6 to 30 carbon atoms.

According to an exemplary embodiment of the present specification, in Formula 1, R1 is hydrogen; Or a monocyclic or polycyclic aryl group having 6 to 20 carbon atoms.

According to an exemplary embodiment of the present specification, in Formula 1, R1 is hydrogen; Or a monocyclic or polycyclic aryl group having 6 to 10 carbon atoms.

According to an exemplary embodiment of the present specification, in Formula 1, R1 is hydrogen; Phenyl group; Or a naphthyl group.

According to an exemplary embodiment of the present specification, in Formula 1, r1 is 1.

According to an exemplary embodiment of the present specification, in Formula 1, R2 is hydrogen.

According to an exemplary embodiment of the present specification, in Formula 1, r2 is 0.

According to an exemplary embodiment of the present specification, in Formula 1, r2 is 8.

According to an exemplary embodiment of the present specification, in Formula 1, R3 is hydrogen.

According to an exemplary embodiment of the present specification, in Formula 1, r3 is 0.

According to an exemplary embodiment of the present specification, in Formula 1, r3 is 4.

According to an exemplary embodiment of the present specification, in Formula 1, Ar1 is a monocyclic or polycyclic aryl group having 6 to 30 carbon atoms; Or a C 2 to C 30 heteroaryl group substituted or unsubstituted with a C 6 to C 30 monocyclic or polycyclic aryl group.

According to an exemplary embodiment of the present specification, in Formula 1, Ar1 is a monocyclic or polycyclic aryl group having 6 to 20 carbon atoms; Or a C 2 to C 20 heteroaryl group unsubstituted or substituted with a C 6 to C 12 monocyclic aryl group.

According to an exemplary embodiment of the present specification, in Formula 1, Ar1 is a phenyl group; Naphthyl group; Phenanthrene group; Triphenylene group; Fluoranthene group; Pyren group; Dibenzofuran group; Dibenzothiophene group; Or a carbazole group substituted with a phenyl group.

According to an exemplary embodiment of the present specification, Formula 1 is selected from the following compounds.

According to an exemplary embodiment of the present specification, in Formula 2, A1 to A3 are the same as or different from each other, and each independently is a 1 to 5 ring ring.

According to an exemplary embodiment of the present specification, in Formula 2, A1 to A3 are the same as or different from each other, and each independently is a 1 to 4 ring ring.

According to an exemplary embodiment of the present specification, in Formula 2, A1 to A3 are the same as or different from each other, and each independently is a 1 to 3 ring ring.

According to an exemplary embodiment of the present specification, in Formula 2, A1 to A3 are the same as or different from each other, and each independently a monocyclic ring having 2 to 6 carbon atoms or a polycyclic ring having 6 to 26 carbon atoms.

According to an exemplary embodiment of the present specification, in Formula 2, A1 to A3 are the same as or different from each other, and each independently a monocyclic ring having 2 to 6 carbon atoms or a polycyclic ring having 6 to 22 carbon atoms.

According to an exemplary embodiment of the present specification, in Formula 2, A1 to A3 are the same as or different from each other, and each independently a monocyclic ring having 2 to 6 carbon atoms or a polycyclic ring having 6 to 18 carbon atoms.

According to an exemplary embodiment of the present specification, in Formula 2, G1 to G3 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Alkyl group; Aryl group; Heteroaryl group; Alkylamine group; An arylamine group unsubstituted or substituted with an alkyl group or an alkylsilyl group; Or a heteroarylamine group. Here, the alkylsilyl group means a silyl group substituted with an alkyl group, and may be, for example, a trimethylsilyl group.

According to an exemplary embodiment of the present specification, in Chemical Formula 2, G1 to G3 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; An alkyl group having 1 to 15 carbon atoms; Aryl group having 6 to 25 carbon atoms; A heteroaryl group having 2 to 24 carbon atoms; An alkylamine group having 1 to 20 carbon atoms; An arylamine group having 6 to 25 carbon atoms unsubstituted or substituted with an alkyl group or an alkylsilyl group; Or a C2-C24 heteroarylamine group. Combined with a group to form a substituted or unsubstituted C5 to C20 ring.

According to an exemplary embodiment of the present specification, in Chemical Formula 2, G1 to G3 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; An alkyl group having 1 to 10 carbon atoms; Aryl group having 6 to 22 carbon atoms; A heteroaryl group having 2 to 20 carbon atoms; An alkylamine group having 1 to 15 carbon atoms; An arylamine group having 6 to 22 carbon atoms unsubstituted or substituted with an alkyl group or an alkylsilyl group; Or it is a C2-C20 heteroarylamine group.

According to an exemplary embodiment of the present specification, in Formula 2, G1 to G3 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; An alkyl group having 1 to 6 carbon atoms; Aryl group having 6 to 18 carbon atoms; A heteroaryl group having 2 to 18 carbon atoms; An alkylamine group having 1 to 10 carbon atoms; An arylamine group having 6 to 20 carbon atoms unsubstituted or substituted with an alkyl group or an alkylsilyl group; Or it is a C2-C18 heteroarylamine group.

According to an exemplary embodiment of the present specification, Formula 2 is represented by any one of the following Formulas 2-1 to 2-6.

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Formula 2-4]

[Formula 2-5]

[Formula 2-6]

In Formulas 2-1 to 2-6,

The definitions of X, Y1 to Y3 and A1 to A3 are the same as defined in Formula 2,

A4 and A5 are the same as or different from each other, and each independently a monocyclic or polycyclic ring,

Y4 and Y5 are the same as or different from each other, and each independently a direct bond; O; C(Rm)(Rn); Or N(Rp),

Y6 and Y7 are N,

Rm, Rn and Rp are the same as or different from each other, and each independently hydrogen, deuterium, an alkyl group, or a substituted or unsubstituted aryl group, or combine with an adjacent group to form a substituted or unsubstituted ring,

T1 to T5 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Alkyl group; Aryl group; Heteroaryl group; Alkylamine group; A substituted or unsubstituted arylamine group; Or a heteroarylamine group,

c1 to c5 are each an integer greater than or equal to 0,

When each of c1 to c5 is 2 or more, the structures in the two or more parentheses are the same or different from each other.

According to an exemplary embodiment of the present specification, A4 and A5 are the same as or different from each other, and each independently is a 1 to 5 ring ring.

According to an exemplary embodiment of the present specification, A4 and A5 are the same as or different from each other, and each independently is a 1 to 4 ring ring.

According to an exemplary embodiment of the present specification, A4 and A5 are the same as or different from each other, and each independently is a 1 to 3 ring ring.

According to the exemplary embodiment of the present specification, A4 and A5 are the same as or different from each other, and are each independently a monocyclic ring having 2 to 6 carbon atoms, or a polycyclic ring having 6 to 26 carbon atoms.

According to an exemplary embodiment of the present specification, A4 and A5 are the same as or different from each other, and each independently a monocyclic ring having 2 to 6 carbon atoms or a polycyclic ring having 6 to 22 carbon atoms.

According to the exemplary embodiment of the present specification, A4 and A5 are the same as or different from each other, and each independently a monocyclic ring having 2 to 6 carbon atoms, or a polycyclic ring having 6 to 18 carbon atoms.

,

,

,

,

또는

이다.According to an exemplary embodiment of the present specification, A4 and A5 are the same as or different from each other, and each independently benzene, naphthalene, triphenylene, 9,9'-spirobifluorene, dibenzofuran, dibenzothiophene, Dibenzoselenophene, carbazole, indolocarbazole, naphthobenzofuran,

,

,

,

,

or

to be.

According to an exemplary embodiment of the present specification, A4 and A5 are each benzene.

According to an exemplary embodiment of the present specification, Y3 is C(Rm)(Rn); N(Rp); Or a substituted or unsubstituted silyl group.

According to an exemplary embodiment of the present specification, Y3 is C(Rm)(Rn); N(Rp); Or a silyl group unsubstituted or substituted with an aryl group.

According to an exemplary embodiment of the present specification, Y3 is C(Rm)(Rn); N(Rp); Or it is a silyl group substituted with a phenyl group.

According to an exemplary embodiment of the present specification, Rm and Rn are the same as or different from each other, and each independently hydrogen, deuterium, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 18 carbon atoms, or combined with each other to have 5 to carbon atoms 17 rings.

According to an exemplary embodiment of the present specification, Rm and Rn combine with each other to form a fluorene ring.

According to an exemplary embodiment of the present specification, Rp is hydrogen, deuterium, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkylaryl group having 7 to 30 carbon atoms.

According to an exemplary embodiment of the present specification, Rp is hydrogen, deuterium, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an alkylaryl group having 7 to 25 carbon atoms.

According to an exemplary embodiment of the present specification, Rp is a phenyl group; A phenyl group substituted with at least one selected from a methyl group, a t-butyl group, a phenyl group, and an alkylphenyl group; Or a naphthyl group.

According to an exemplary embodiment of the present specification, Formula 2 is represented by any one of the following Formulas 3-1 to 3-7.

[Formula 3-1]

[Chemical Formula 3-2]

[Chemical Formula 3-3]

[Formula 3-4]

[Formula 3-5]

[Formula 3-6]

[Formula 3-7]

In Formulas 3-1 to 3-7,

The definition of X and A1 to A3 is the same as defined in Formula 2,

A4 and A5 are the same as or different from each other, and each independently a monocyclic or polycyclic ring,

T1 to T5 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Alkyl group; Aryl group; Heteroaryl group; Alkylamine group; A substituted or unsubstituted arylamine group; Or a heteroarylamine group,

c1 to c5 are each an integer greater than or equal to 0,

When each of the c1 to c5 is 2 or more, the structures in the two or more parentheses are the same or different from each other,

Rp ₁ to Rp ₃ are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Alkyl group; Or a substituted or unsubstituted aryl group,

Rm ₃ to Rm ₅ And Rn ₃ to Rn ₅ are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Alkyl group; Or an aryl group, or combine with each other to form a ring.

According to an exemplary embodiment of the present specification, Rp ₁ to Rp ₃ are the same as or different from each other, and each independently hydrogen, deuterium, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkyl having 7 to 30 carbon atoms. It is an aryl group.

According to an exemplary embodiment of the present specification, Rp ₁ to Rp ₃ are the same as or different from each other, and each independently hydrogen, deuterium, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms, or a 7 to 25 carbon atom. It is an alkylaryl group.

According to an exemplary embodiment of the present specification, Rp ₁ to Rp ₃ are the same as or different from each other, and each independently a phenyl group; A phenyl group substituted with at least one selected from a methyl group, a t-butyl group, a phenyl group, and an alkylphenyl group; Or a naphthyl group.

According to an exemplary embodiment of the present specification, Rm ₃ to Rm ₅ and Rn ₃ to Rn ₅ are the same as or different from each other, and each independently hydrogen, deuterium, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 18 carbon atoms Or combine with each other to form a ring having 5 to 17 carbon atoms.

According to an exemplary embodiment of the present specification, Rm ₃ and Rn ₃ are bonded to each other to form a fluorene ring.

According to an exemplary embodiment of the present specification, Rm ₄ and Rn ₄ are bonded to each other to form a fluorene ring.

According to an exemplary embodiment of the present specification, Rm ₅ and Rn ₅ are bonded to each other to form a fluorene ring.

,

,

,

,

또는

이다.According to an exemplary embodiment of the present specification, in Formula 2, A1 to A3 are the same as or different from each other, and each independently benzene, naphthalene, triphenylene, 9,9'-spirobifluorene, dibenzofuran, Dibenzothiophene, dibenzoselenophene, carbazole, indolocarbazole, naphthobenzofuran,

,

,

,

,

or

to be.

According to an exemplary embodiment of the present specification, A1 to A3 are the same as or different from each other, and each independently benzene, naphthalene, dibenzofuran, dibenzothiophene, or carbazole.

According to an exemplary embodiment of the present specification, T1 to T5 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; An alkyl group having 1 to 10 carbon atoms; Aryl group of 6 to 22 carbon atoms; A heteroaryl group having 2 to 20 carbon atoms; An alkylamine group having 1 to 10 carbon atoms; An arylamine group having 6 to 18 carbon atoms unsubstituted or substituted with an alkyl group or an alkylsilyl group; Or it is a C2-C20 heteroarylamine group.

According to an exemplary embodiment of the present specification, T1 to T5 are the same as or different from each other, and each independently hydrogen; An alkyl group having 1 to 6 carbon atoms; Aryl group of 6 to 18 carbon atoms; Or a C 2 to C 16 heteroaryl group; An alkylamine group having 1 to 6 carbon atoms; Arylamine group of 6 to 18 carbon atoms unsubstituted or substituted with an alkyl group or an alkylsilyl group; Or a C2-C16 heteroarylamine group.

According to an exemplary embodiment of the present specification, T1 to T5 are the same as or different from each other, and each independently hydrogen; Methyl group; t-butyl group; a diphenylamine group unsubstituted or substituted with a t-butyl group or a trimethylsilyl group; Or a carbazolyl group.

According to an exemplary embodiment of the present specification, c1 is 0 or 1.

According to an exemplary embodiment of the present specification, c2 is 0 or 1.

According to an exemplary embodiment of the present specification, c3 is 0 or 1.

According to an exemplary embodiment of the present specification, c4 is 0 or 1.

According to an exemplary embodiment of the present specification, c5 is 0 or 1.

According to an exemplary embodiment of the present specification, the sum of c1 to c5 is 1 or more.

According to an exemplary embodiment of the present specification, Formula 2 is selected from the following compounds.

According to an exemplary embodiment of the present specification, in Formula 1, the emission layer includes a compound represented by Formula 1 and a compound represented by Formula 2, and Formula 1: Formula 2 is of 50:50 to 99:1 Included in weight ratio.

When the light emitting layer contains the above formulas 1 and 2 in the weight ratio, electrons and holes can be effectively introduced, an energy transfer system is formed, and self-extinguishing can be reduced to a minimum, thereby providing an organic light emitting device having a long lifespan and a high efficiency. There are features that can be obtained.

According to an exemplary embodiment of the present specification, Chemical Formula 1 is a host of an emission layer.

The structure of Formula 1 facilitates the flow of electrons and increases steric hindrance, reducing the phenomenon of accumulation of each molecule too close, so that the structure of the thin film is stable, so an organic light emitting device including this as a host of the emission layer Has the effect of long life.

According to an exemplary embodiment of the present specification, Chemical Formula 2 is a dopant of the emission layer.

According to the exemplary embodiment of the present specification, the maximum emission wavelength of the dopant is 440nm to 480nm.

According to the exemplary embodiment of the present specification, the dopant is a blue dopant.

The structure of Formula 2 includes a ring of A1 to A3 with X as the center, and has a stabilized form by transferring electrons to X, which lacks electrons, by forming a rigid ring through Y1 and Y2. In addition, the compound represented by Chemical Formula 2 has a narrow half-width of the emission spectrum, and an organic light-emitting device including the compound as a dopant of the emission layer has high luminous efficiency and excellent color reproducibility.

According to an exemplary embodiment of the present specification, the compounds of Formulas 1 and 2 may be prepared using starting materials and reaction conditions known in the art. The type and number of substituents can be determined by appropriately selecting a known starting material by a person skilled in the art. In addition, the compounds of Formulas 1 and 2 may be obtained from commercially available ones.

According to the exemplary embodiment of the present specification, the organic light emitting device may include only the aforementioned emission layer as an organic material layer, but may further include an additional organic material layer. For example, an additional hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, and the like may be further included.

The organic light-emitting device may further include an additional blue light-emitting layer, and may further include one or more of green and red light-emitting layers other than blue, thereby forming a white organic light-emitting device.

For example, the structure of the organic light-emitting device of the present specification may have a structure as shown in FIGS. 1 and 2, but is not limited thereto.

1 illustrates a structure of an organic light emitting diode 10 in which a first electrode 30, a light emitting layer 40, and a second electrode 50 are sequentially stacked on a substrate 20. 1 is an exemplary structure according to an exemplary embodiment of the present specification, and may further include another organic material layer.

2 shows a first electrode 30, a hole injection layer 60, a hole transport layer 70, a light emitting layer 40, an electron transport layer 80, an electron injection layer 90, and a second electrode on the substrate 20. The structure of the organic light-emitting device 11 in which 50) are sequentially stacked is illustrated. 2 is an exemplary structure according to the exemplary embodiment of the present specification, and may further include another organic material layer.

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.

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.

The organic light-emitting device of the present specification may be manufactured by materials and methods known in the art, except that the emission layer includes the compound represented by Formula 1 and the compound represented by Formula 2.

For example, the organic light emitting device of the present specification may be manufactured by sequentially laminating a first electrode, an organic material layer, and a second electrode on a substrate. At this time, by using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation, a metal or a conductive metal oxide or an alloy thereof is deposited on the substrate. It can be manufactured by forming a first electrode, forming an organic material layer including a hole injection layer, a hole transport layer, an emission layer, and an electron transport layer thereon, and then depositing a material that can be used as a second electrode thereon. In addition to such a method, an organic light-emitting device may be manufactured by sequentially depositing a second electrode material, an organic material layer, and a first electrode material on a substrate. In addition, the compound of Formula 1 or 2 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.

According to an exemplary embodiment of the present specification, the first electrode is an anode, and the second electrode is a cathode.

According to another exemplary embodiment of the present specification, 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 a multilayered material such as LiF/Al, LiO ₂ /Al, and Mg/Ag, but are not limited thereto.

The hole injection layer is a layer that injects holes from an electrode, and has the ability to transport holes as a hole injection material, so that it has a hole injection effect at the anode, an excellent hole injection effect for a light emitting layer or a light emitting material. 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, etc., 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 electron blocking layer is a layer capable of improving the life and efficiency of the device by preventing electrons injected from the electron injection layer from entering the hole injection layer through the light emitting layer, and when necessary, a light emitting layer and a hole are used. It may be formed in an appropriate portion between the injection layer.

When the organic light-emitting device of the present specification includes an additional light-emitting layer other than the light-emitting layer including Formulas 1 and 2, the light-emitting material of the light-emitting layer is visible light by transporting and combining holes and electrons from the hole transport layer and the electron transport layer, respectively. As a material capable of emitting light in a region, 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, benzothiazole, and benzimidazole-based compounds; Poly(p-phenylenevinylene) (PPV)-based polymer; Spiro compounds; Polyfluorene, rubrene, and the like, but are not limited thereto.

The light emitting layer may include an additional host material and a dopant material. Host materials include condensed aromatic ring derivatives or hetero ring-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 carbazole derivatives, dibenzofuran derivatives, ladder type Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.

The hole blocking layer is a layer capable of improving the life and efficiency of the device by preventing holes injected from the hole injection layer from entering the electron injection layer through the light emitting layer, and when necessary, a light emitting layer and an electron It may be formed in an appropriate portion between the injection layer.

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 receiving electrons from the cathode and transferring them to the emission layer is a material having high mobility for electrons. Suitable. 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 ring 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 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.

The structure according to the exemplary embodiment of the present specification may act on a principle similar to that applied to an organic light-emitting device in organic electronic devices including organic solar cells, organic photoreceptors, and organic transistors.

Hereinafter, examples will be described in detail in order to describe the present specification in detail. However, the embodiments according to the present specification may be modified in various forms, and the scope of the present specification is not construed as being limited to the embodiments described below. The embodiments of the present specification are provided to more completely describe the present specification to those of ordinary skill in the art.

<Synthesis Example>

Synthesis Example 1. Synthesis of Compound 1-1

9-Bromoanthracene (100g, 388.9mmol) and dibenzofuran-1-ylboronic acid (90.7g, 427.8mmol) were placed in a round bottom flask and dissolved in 1500 mL of dioxane. Potassium phosphate (K ₃ PO ₄ ; 206.4 g, 972.3 mmol) was dissolved in 300 mL of pure water and added, and bis(trit-butylphosphine)palladium(0)(tBu ₃ P) ₂ Pd; 398mg, 0.778mmol) was added. Refluxed for 2 hours, cooled, and filtered. The filtered solid was recrystallized from toluene to obtain 1-(anthracene-9-yl)dibenzofuran (113.9g, 330.6 mmol).

1-(anthracene-9-yl)dibenzofuran (100g, 290.4mmol) was dissolved in dried dimethylformamide (DMF; 1000mL) and cooled to 0°C. N-bromosuccinimide (NBS; 54.3 g, 304.8 mmol) was slowly added and stirred for 2 hours. The reaction solution was added to water (2.5L) in excess, and the precipitated solid was filtered. The filtered solid was recrystallized from toluene to obtain 1-(10-bromoanthracene-9-yl)dibenzofuran (110.1 g, 260.1 mmol).

1-(10-bromoanthracene-9-yl)dibenzofuran (20.0g, 47.2mmol) and [1,1'-biphenyl]-2-ylboronic acid (10.3g, 52.0mmol) in a round bottom flask Then, it was dissolved in 400 mL of dioxane. Potassium phosphate (25.1 g, 118.1 mmol) was dissolved in 100 mL of pure water and added, and bis (trit-butylphosphine) palladium (0) (48 mg, 0.094 mmol) was added. Refluxed for 2 hours, cooled, and filtered. The filtered solid was recrystallized from toluene to obtain compound 1-1 (13.2 g, 38.3 mmol).

Synthesis Examples 2 to 10. Synthesis of Compounds 1-21, 2-10, 3-1, 3-19, 4-12, 5-5, 13-20, 20-11 and 29-1

Compound 1 in the same procedure as in Synthesis Example 1 except that the compounds of Table 1 below were used instead of dibenzofuran-1-ylboronic acid and [1,1′-biphenyl]-2-ylboronic acid in Synthesis Example 1, respectively. -21, 2-10, 3-1, 3-19, 4-12, 5-5, 13-20, 20-11 and 29-1 were synthesized, respectively.

No. Target compound Use instead of the following compound of Synthesis Example Dibenzofuran-1-ylboronic acid [1,1'-biphenyl]-2-ylboronic acid Synthesis Example 2 Compound 1-21 (4-(dibenzofuran-1-yl)phenyl)boronic acid (2-(naphthalen-1-yl)phenyl)boronic acid Synthesis Example 3 Compound 2-10 Dibenzofuran-2-ylboronic acid (2-(dibenzofuran-3-yl)phenyl)boronic acid Synthesis Example 4 Compound 3-1 Dibenzofuran-3-ylboronic acid [1,1'-biphenyl]-2-ylboronic acid Synthesis Example 5 Compound 3-19 Dibenzofuran-3-ylboronic acid (2-(9-phenyl-9H-carbazol-1-yl)phenyl)boronic acid Synthesis Example 6 Compound 4-12 Dibenzofuran-4-ylboronic acid (2-(dibenzothiophen-1-yl)phenyl)boronic acid Synthesis Example 7 Compound 5-5 (2-phenyldibenzofuran-1-yl) boronic acid (2-(triphenylen-2-yl)phenyl)boronic acid Synthesis Example 8 Compound 13-20 (3-(naphthalen-2-yl)dibenzofuran-2-yl)boronic acid (2-(Fluoranthen-3-yl)phenyl)boronic acid Synthesis Example 9 Compound 20-11 (2-(naphthalen-1-yl)dibenzofuran-3-yl)boronic acid (2-(phenanthrene-9-yl)phenyl)boronic acid Synthesis Example 10 Compound 29-1 (9-phenyldibenzofuran-4-yl) boronic acid [1,1'-biphenyl]-2-ylboronic acid

The structures of the compounds synthesized in Synthesis Examples 1 to 10 are shown in Table 2 below.

Synthesis Example 11. Synthesis of Compound BD-1

N1,N1,N3,N3-tetrakis(4-(t-butyl)phenyl)-2-chloro-N5,N5-diphenylbenzene-1,3,5-tri in 500 mL of anhydrous toluene (Tol) under a nitrogen atmosphere The amine (30.0g, 35.7mmol) was dissolved and cooled to 0°C. 84.2 mL of t-butyllithium (tBuLi; 1.7M pentane solution; 143.1 mmol) was slowly added dropwise, followed by stirring at 60° C. for 3 hours. After cooling to 0°C again, boron tribromide (BBr ₃ ; 17.9g, 71.5mmol) was slowly added dropwise, followed by stirring at 70°C for 10 hours. After completion of the reaction, the reaction solution was cooled to room temperature, a saturated ammonium hydrochloride solution was added to separate the mixture, and the organic layer was dried over anhydrous magnesium sulfate. The obtained solution was concentrated under reduced pressure and recrystallized with toluene and hexane to obtain the compound BD-1 (5.2 g, 6.4 mmol).

Synthesis Examples 12 to 22. Compounds BD-2, BD-4, BD-6, BD-7, BD-11, BD-14, BD-18, BD-20, BD-21, BD-26 and BD -27 synthesis

Table 3 below instead of N1,N1,N3,N3-tetrakis(4-(t-butyl)phenyl)-2-chloro-N5,N5-diphenylbenzene-1,3,5-triamine in Synthesis Example 11 Compounds BD-2, BD-4, BD-6, BD-7, BD-11, BD-14, BD-18, BD-20, BD in the same procedure as in Synthesis Example 11 except that the compounds of each were used -21, BD-26 and BD-27 were synthesized, respectively.

No. Target compound Use instead of the following compound of Synthesis Example 11 N1,N1,N3,N3-tetrakis(4-(t-butyl)phenyl)-2-chloro-N5,N5-diphenylbenzene-1,3,5-triamine Synthesis Example 12 Compound BD-2 2-Chloro-5-methyl-N1,N1,N3,N3-tetra-p-tolylbenzene-1,3-diamine Synthesis Example 13 Compound BD-4 N1,N1,N3,N3-tetrakis(4-(t-butyl)phenyl)-2-chloro-N5-phenyl-N5-(4-(trimethylsilyl)phenyl)benzene-1,3,5-triamine Synthesis Example 14 Compound BD-6 2-Chloro-N5,N5-diphenyl-N1,N1,N3,N3-tetra-p-tolylbenzene-1,3,5-triamine Synthesis Example 15 Compound BD-7 N1,N1,N3,N3-tetrakis(4-(t-butyl)phenyl)-2-chloro-5-methylbenzene-1,3-diamine Synthesis Example 16 Compound BD-11

3 ² -Chloro-1 ⁵ ,3 ⁵ ,5 ⁵ -trimethyl-2,4,6,6-tetraphenyl-2,4-diaza-6-sila-1,3,5(1,3)-tri Benzenacyclohexaphane

Synthesis Example 17 Compound BD-14 N,N-bis(4-(t-butyl)phenyl)-4-chloro-3,5-bis(4a,9a-dimethyl-1,2,3,4,4a,9a-hexahydro-9H-carba Zol-9-yl)aniline Synthesis Example 18 Compound BD-18 9-(2'-chlorospiro[fluorene-9,6'-2,4-dioxa-1,3,5(1,3)-tribenzenacyclohexaphan]-5'-yl)-9H -Carbazole Synthesis Example 19 Compound BD-20 2-Chloro-N1,N1,N3,N3,N5,N5-hexa-p-tolylbenzene-1,3,5-triamine Synthesis Example 20 Compound BD-21 N,N-bis(3-(t-butyl)phenyl)-2-chloro-3-(4a,9a-dimethyl-1,2,3,4,4a,9a-hexahydro-9H-carbazole-9 -Yl)-5-methylaniline Synthesis Example 21 Compound BD-26 N1,N1,N3-tris(4-(t-butyl)phenyl)-2-chloro-5-methyl-N3-(5-(2-phenylpropan-2-yl)-[1,1'-biphenyl ]-2-yl)benzene-1,3-diamine Synthesis Example 22 Compound BD-27 N1,N1,N3-tris(4-(t-butyl)phenyl)-2-chloro-N3-(4',5-di-t-butyl-[1,1'-biphenyl]-2-yl) -5-methylbenzene-1,3-diamine

The mass spectrum analysis results of the compounds synthesized in Synthesis Examples 1 to 22 are shown in Table 4 below.

Molecular Weight m/z [M+H]+ Compound 1-1 496.61 497.38 Compound 1-21 622.77 623.63 Compound 2-10 586.69 588.08 Compound 3-1 496.61 497.75 Compound 3-19 661.80 662.75 Compound 4-12 602.75 604.11 Compound 5-5 722.89 724.18 Compound 13-20 746.91 747.96 Compound 20-11 722.89 723.79 Compound 29-1 572.71 573.89 BD-1 811.97 813.17 BD-2 490.46 491.15 BD-4 884.15 884.99 BD-6 643.64 644.87 BD-7 658.78 660.09 BD-11 642.68 644.01 BD-14 763.92 765.25 BD-18 597.48 598.84 BD-20 671.70 672.48 BD-21 578.65 579.29 BD-26 796.95 798.05 BD-27 790.99 791.68

<Example: Fabrication of organic light emitting device>

Comparative Example 1.

A glass substrate coated with a thin film of 1,500Å of indium tin oxide (ITO) was put in distilled water dissolved in a detergent and washed with ultrasonic waves. In this case, Fischer Co. product 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, ultrasonic washing was performed for 10 minutes by repeating twice with distilled water. After washing with distilled water, ultrasonic cleaning 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, hexanitrile hexaazatriphenylene (HAT) of the following formula was thermally vacuum deposited to a thickness of 500 Å to form a hole injection layer.

(HAT)

(HAT)

On the hole injection layer, 4,4'-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (NPB) (400Å) of the following formula, which is a material for transporting holes, was vacuum deposited to form a hole transport layer. Formed.

(NPB)

(NPB)

Subsequently, (naphthalen-1-yl)-10-(4-(naphthalen-2-yl)phenyl)anthracene (BH-A) was vacuum deposited to a thickness of 300 Å as a host of the emission layer on the hole transport layer to form a light emitting layer. .

(BH-A)

(BH-A)

4,4'-(pyrene-1,6-diylbis(phenylazanediyl))dibenzonitrile (BD-A) was used as a blue light-emitting dopant while depositing the emission layer.

(BD-A)

(BD-A)

Alq ₃ (aluminum tris (8-hydroxyquinoline)) of the following formula was vacuum-deposited to a thickness of 200 Å on the emission layer to form an electron injection and transport layer.

(Alq3)

(Alq3)

Lithium fluoride (LiF) in a thickness of 12 Å and aluminum in a thickness of 2,000 Å were sequentially deposited on the electron injection and transport layer to form a negative electrode.

In the above process, the deposition rate of the organic material was maintained at 0.4 Å/sec to 0.7 Å/sec, lithium fluoride at the cathode was maintained at 0.3 Å/sec, and the deposition rate for aluminum was 2 Å/sec, and the vacuum degree during deposition was 2 × 10 ^-7 torr to 5Х10 ^-8 torr was maintained.

Comparative Examples 2 to 24.

The organic light emitting device of Comparative Examples 2 to 24 in the same manner as in Comparative Example 1, except that the compounds of Table 5 below were used instead of BH-A and BD-A as hosts and dopants of the emission layer in Comparative Example 1 Was prepared.

Host Dopant Comparative Example 1 BH-A BD-A Comparative Example 2 BH-A BD-B Comparative Example 3 BH-A BD-1 Comparative Example 4 BH-A BD-20 Comparative Example 5 BH-B BD-A Comparative Example 6 BH-B BD-B Comparative Example 7 BH-B BD-1 Comparative Example 8 BH-B BD-20 Comparative Example 9 BH-C BD-A Comparative Example 10 BH-C BD-B Comparative Example 11 BH-C BD-E Comparative Example 12 BH-C BD-F Comparative Example 13 BH-C BD-1 Comparative Example 14 BH-C BD-20 Comparative Example 15 BH-D BD-1 Comparative Example 16 BH-D BD-20 Comparative Example 17 BH-E BD-1 Comparative Example 18 BH-E BD-20 Comparative Example 19 1-1 BD-A Comparative Example 20 1-1 BD-C Comparative Example 21 1-1 BD-D Comparative Example 22 3-1 BD-A Comparative Example 23 3-1 BD-C Comparative Example 24 3-1 BD-D

The structures of the host and the dopant used in the comparative example are shown in Table 6 below.

Preparation of Examples 1 to 40.

Organic light-emitting devices of Examples 1 to 40 in the same manner as in Comparative Example 1, except that the compounds of Table 7 below were used instead of BH-A and BD-A as hosts and dopants of the emission layer in Comparative Example 1 Was prepared.

Host Dopant Example 1 Compound 1-1 BD-1 Example 2 Compound 1-1 BD-2 Example 3 Compound 1-21 BD-1 Example 4 Compound 1-21 BD-2 Example 5 Compound 1-21 BD-4 Example 6 Compound 2-10 BD-1 Example 7 Compound 2-10 BD-2 Example 8 Compound 2-10 BD-4 Example 9 Compound 2-10 BD-6 Example 10 Compound 2-10 BD-7 Example 11 Compound 3-1 BD-2 Example 12 Compound 3-1 BD-4 Example 13 Compound 3-1 BD-6 Example 14 Compound 3-1 BD-7 Example 15 Compound 3-1 BD-11 Example 16 Compound 3-19 BD-6 Example 17 Compound 3-19 BD-7 Example 18 Compound 3-19 BD-11 Example 19 Compound 3-19 BD-14 Example 20 Compound 3-19 BD-18 Example 21 Compound 4-12 BD-7 Example 22 Compound 4-12 BD-11 Example 23 Compound 4-12 BD-14 Example 24 Compound 4-12 BD-18 Example 25 Compound 4-12 BD-20 Example 26 Compound 5-5 BD-14 Example 27 Compound 5-5 BD-18 Example 28 Compound 5-5 BD-20 Example 29 Compound 5-5 BD-21 Example 30 Compound 5-5 BD-26 Example 31 Compound 13-20 BD-18 Example 32 Compound 13-20 BD-20 Example 33 Compound 13-20 BD-21 Example 34 Compound 13-20 BD-26 Example 35 Compound 13-20 BD-27 Example 36 Compound 20-11 BD-21 Example 37 Compound 20-11 BD-26 Example 38 Compound 20-11 BD-27 Example 39 Compound 29-1 BD-26 Example 40 Compound 29-1 BD-27

For the organic light emitting devices of the Comparative Examples and Examples, the results of measuring the performance such as voltage, luminous efficiency, color coordinates, and lifetime at a current density of 20 mA/cm ² are shown in Table 8 below. T97% is a measure of the time when the luminance becomes 97% of the initial luminance.

Element example Driving voltage
(V) Luminous efficiency
(Cd/A) Color coordinate CIE_y Life T97%
(time) Comparative Example 1 5.29 6.71 0.046 77 Comparative Example 2 5.32 6.85 0.045 91 Comparative Example 3 5.28 7.10 0.043 67 Comparative Example 4 5.25 7.15 0.041 71 Comparative Example 5 5.31 6.59 0.046 85 Comparative Example 6 5.28 6.70 0.045 95 Comparative Example 7 5.27 7.09 0.042 83 Comparative Example 8 5.31 7.11 0.042 74 Comparative Example 9 5.54 6.50 0.046 83 Comparative Example 10 5.49 6.58 0.045 90 Comparative Example 11 5.41 5.13 0.042 24 Comparative Example 12 5.46 5.49 0.043 18 Comparative Example 13 5.52 6.91 0.042 81 Comparative Example 14 5.47 6.85 0.041 76 Comparative Example 15 5.11 6.89 0.043 85 Comparative Example 16 5.09 6.72 0.040 82 Comparative Example 17 5.11 6.91 0.043 69 Comparative Example 18 5.05 6.93 0.041 76 Comparative Example 19 5.08 5.51 0.044 93 Comparative Example 20 5.02 5.13 0.052 7 Comparative Example 21 5.07 5.41 0.091 22 Comparative Example 22 5.12 6.31 0.044 81 Comparative Example 23 5.17 6.02 0.055 6 Comparative Example 24 5.13 6.16 0.093 35 Example 1 5.06 7.53 0.044 114 Example 2 5.21 7.47 0.041 134 Example 3 5.16 7.22 0.042 116 Example 4 5.18 7.59 0.042 140 Example 5 5.20 7.36 0.042 139 Example 6 4.89 7.54 0.040 123 Example 7 4.93 7.28 0.041 139 Example 8 5.07 7.24 0.044 125 Example 9 4.99 7.40 0.043 141 Example 10 4.98 7.37 0.044 113 Example 11 5.25 7.48 0.041 107 Example 12 5.02 7.26 0.044 128 Example 13 5.01 7.41 0.044 141 Example 14 5.13 7.27 0.040 146 Example 15 5.22 7.21 0.040 136 Example 16 4.83 7.21 0.041 130 Example 17 4.84 7.43 0.044 119 Example 18 4.99 7.58 0.042 105 Example 19 5.00 7.23 0.043 107 Example 20 5.09 7.55 0.043 116 Example 21 5.00 7.42 0.041 107 Example 22 4.83 7.26 0.040 113 Example 23 4.83 7.24 0.044 101 Example 24 4.97 7.50 0.041 115 Example 25 4.93 7.48 0.043 103 Example 26 5.23 7.33 0.040 101 Example 27 5.13 7.26 0.043 126 Example 28 5.23 7.54 0.040 133 Example 29 5.16 7.42 0.042 142 Example 30 5.24 7.37 0.043 118 Example 31 5.10 7.32 0.042 144 Example 32 5.05 7.41 0.042 100 Example 33 5.22 7.31 0.043 139 Example 34 5.26 7.27 0.043 134 Example 35 4.95 7.23 0.044 121 Example 36 5.20 7.45 0.042 106 Example 37 5.25 7.32 0.043 133 Example 38 5.23 7.27 0.044 129 Example 39 4.93 7.42 0.042 111 Example 40 5.17 7.25 0.043 110

Looking at the results in Table 8, Examples 1 to 40 in which the compound represented by Formula 1 was used as the host of the emission layer and the compound represented by Formula 2 was used as the dopant for the emission layer according to an exemplary embodiment of the present specification Compared to Examples 1 to 24, it can be seen that the driving voltage is low, and features high efficiency and long lifespan.

10, 11: organic light emitting device
20: substrate
30: first electrode
40: light emitting layer
50: second electrode
60: hole injection layer
70: hole transport layer
80: electron transport layer
90: electron injection layer

Claims (12)

A first electrode;
A second electrode provided opposite to the first electrode; And
An organic light-emitting device provided between the first electrode and the second electrode and including a light-emitting layer including a compound represented by Formula 1 and a compound represented by Formula 2:
[Formula 1]

In Formula 1,
L1 is a phenylene group,
R1 to R3 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; Cyano group; Alkyl group; Cycloalkyl group; Alkenyl group; Alkoxy group; Aryloxy group; Amine group; Aryl group; Or a heteroaryl group,
Ar1 is a naphthyl group; Phenanthrene group; Triphenylene group; Fluoranthene group; Pyren group; Or a heteroaryl group unsubstituted or substituted with an aryl group,
r1 is an integer from 0 to 7,
r2 is an integer from 0 to 8,
r3 is an integer from 0 to 4,
When each of the r1 to r3 is 2 or more, the structures in the two or more parentheses are the same as or different from each other,
[Formula 2]

In Formula 2,
X is B, P(=O) or P(=S),
A1 to A3 are the same as or different from each other, and each independently a monocyclic or polycyclic ring,
G1 to G3 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Alkyl group; Aryl group; Heteroaryl group; Alkylamine group; A substituted or unsubstituted arylamine group; Or a heteroarylamine group, or may form a ring through Y3 by bonding with an adjacent group,
Y3 is a direct bond; O; C(Rm)(Rn); N(Rp); Or a substituted or unsubstituted silyl group,
Y1 and Y2 are the same as or different from each other, and each independently O or N(Rp),
Rm, Rn and Rp are the same as or different from each other, and each independently hydrogen, deuterium, an alkyl group, or a substituted or unsubstituted aryl group, or combine with an adjacent group to form a substituted or unsubstituted ring,
b1 to b3 are each an integer of 0 or more,
When b1 to b3 are each 2 or more, the structures in the two or more parentheses are the same as or different from each other. delete The method according to claim 1, wherein R1 is hydrogen; Phenyl group; Or an organic light emitting device that is a naphthyl group. The method according to claim 1, wherein Ar1 is a naphthyl group; Phenanthrene group; Triphenylene group; Fluoranthene group; Pyren group; Dibenzofuran group; Dibenzothiophene group; Or an organic light-emitting device that is a carbazole group substituted with a phenyl group. The organic light-emitting device of claim 1, wherein Formula 1 is selected from the following compounds:

. The organic light-emitting device of claim 1, wherein Formula 2 is represented by any one of the following Formulas 2-1 to 2-6:
[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Formula 2-4]

[Formula 2-5]

[Formula 2-6]

In Formulas 2-1 to 2-6,
The definitions of X, Y1 to Y3, Rm, Rn, Rp and A1 to A3 are the same as defined in Formula 2,
A4 and A5 are the same as or different from each other, and each independently a monocyclic or polycyclic ring,
Y4 and Y5 are the same as or different from each other, and each independently a direct bond; O; C(Rm)(Rn); Or N(Rp),
Y6 and Y7 are N,
Rm, Rn and Rp are the same as or different from each other, and each independently hydrogen, deuterium, an alkyl group, or a substituted or unsubstituted aryl group, or combine with an adjacent group to form a substituted or unsubstituted ring,
T1 to T5 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Alkyl group; Aryl group; Heteroaryl group; Alkylamine group; A substituted or unsubstituted arylamine group; Or a heteroarylamine group,
c1 to c5 are each an integer greater than or equal to 0,
When each of c1 to c5 is 2 or more, the structures in the two or more parentheses are the same or different from each other. The organic light-emitting device of claim 1, wherein Formula 2 is represented by any one of the following Formulas 3-1 to 3-7:
[Formula 3-1]

[Chemical Formula 3-2]

[Chemical Formula 3-3]

[Formula 3-4]

[Formula 3-5]

[Formula 3-6]

[Formula 3-7]

In Formulas 3-1 to 3-7,
The definition of X and A1 to A3 is the same as defined in Formula 2,
A4 and A5 are the same as or different from each other, and each independently a monocyclic or polycyclic ring,
T1 to T5 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Alkyl group; Aryl group; Heteroaryl group; Alkylamine group; A substituted or unsubstituted arylamine group; Or a heteroarylamine group,
c1 to c5 are each an integer greater than or equal to 0,
When each of the c1 to c5 is 2 or more, the structures in the two or more parentheses are the same or different from each other,
Rp ₁ to Rp ₃ are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Alkyl group; Or a substituted or unsubstituted aryl group,
Rm ₃ to Rm ₅ And Rn ₃ to Rn ₅ are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Alkyl group; Or an aryl group, or combine with each other to form a ring. The method according to claim 1, wherein A1 to A3 are the same as or different from each other, and each independently benzene, naphthalene, triphenylene, 9,9'-spirobifluorene, dibenzofuran, dibenzothiophene, dibenzoselenophene , Carbazole, indolocarbazole, naphthobenzofuran,

,

,

,

,

or

The organic light emitting device. The organic light-emitting device of claim 1, wherein Formula 2 is selected from the following compounds:

The organic light emitting diode of claim 1, wherein the emission layer comprises a compound represented by Formula 1 and a compound represented by Formula 2, and Formula 1: Formula 2 is included in a weight ratio of 50:50 to 99:1 device. The organic light-emitting device of claim 1, wherein Formula 1 is a host of an emission layer. The organic light-emitting device as set forth in claim 1, wherein Formula 2 is a dopant of an emission layer.

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