KR102254306B1 - Acridine derivative and organic light emitting device comprising the same - Google Patents

Abstract

The present invention provides an acridine derivative represented by Chemical Formula 1 and an organic light-emitting device comprising the same.

Description

An acridine derivative and an organic light-emitting device comprising the same TECHNICAL FIELD [ACRIDINE DERIVATIVE AND ORGANIC LIGHT EMITTING DEVICE COMPRISING THE SAME}

The present specification relates to an acridine derivative and an organic light emitting device including the same.

In general, the organic light emission phenomenon refers to a phenomenon in which electrical energy is converted into light energy by 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 is often made of a multilayer structure composed of different materials in order to increase the efficiency and stability of the organic light emitting device.For example, it 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. 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. When it falls back to the ground, it glows.

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

US Patent Application Publication No. 2004-0251816

The present specification provides an acridine derivative and an organic light emitting device including the same.

According to an exemplary embodiment of the present specification, an acridine derivative represented by the following Chemical Formula 1 is provided.

[Formula 1]

In Formula 1,

R1 and R2 may be hydrogen or bonded to each other,

R3 to R6 are the same as or different from each other, and each independently hydrogen, a nitrile group, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group,

L1 to L3 are the same as or different from each other, and each independently a direct bond or a substituted or unsubstituted arylene group,

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 heteroaryl group, or may be bonded to each other to form a ring,

a is an integer from 0 to 4,

b is an integer from 0 to 7,

c is an integer from 0 to 5,

d is an integer from 0 to 4,

When a is plural, R3 is the same as or different from each other,

When b is plural, R4 is the same as or different from each other,

When c is plural, R5 is the same as or different from each other,

When d is plural, R6 is the same as or different from each other.

In addition, according to an exemplary embodiment of the present specification, the first electrode; A second electrode provided opposite to the first electrode; And one or more organic material layers provided between the first electrode and the second electrode, wherein at least one of the organic material layers comprises an acridine derivative represented by Formula 1 above. Provides.

The acridine derivative according to the exemplary embodiment of the present specification may be used as a material of an organic material layer of an organic light emitting device, and by using the acridine derivative, it is possible to improve efficiency, low driving voltage, and/or lifetime characteristics in the organic light emitting device.

1 illustrates an organic light-emitting device according to an exemplary embodiment of the present specification.
2 illustrates an organic light-emitting device according to another exemplary embodiment of the present specification.
3 illustrates an organic light-emitting device according to an exemplary embodiment of the present specification.

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

The present specification provides an acridine derivative represented by Chemical Formula 1.

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 positioned "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 substituent in the present specification are described below, but are not limited thereto.

The term "substituted" means that the hydrogen atom bonded to the carbon atom of the compound is replaced with another substituent, and the position to be substituted is not limited as long as the position at which 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; Nitrile group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted aryl group; And a substituted or unsubstituted heterocyclic group substituted with one or two or more substituents selected from the group consisting of, or two or more of the substituents exemplified above are substituted with a connected substituent, or does not have any substituents. For example, the "substituent to which two or more substituents are connected" may be an aryl group substituted with an aryl group, an aryl group substituted with a heteroaryl group, a heterocyclic group substituted with an aryl group, an aryl group substituted with an alkyl group, and the like.

In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 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 is preferably 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 alkoxy group may be a straight chain, branched chain, or cyclic chain. Although the number of carbon atoms of the alkoxy group is not particularly limited, it is preferably 1 to 30 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. May be, but is not limited thereto.

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

In the present specification, 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.

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.

In the present specification, the N-alkylheteroarylamine group refers to an amine group in which an alkyl group and a heteroaryl group are substituted with N of the amine group.

In the present specification, the alkyl group in the alkylamine group, N-arylalkylamine group, alkylthioxy group, alkylsulfoxy group, and N-alkylheteroarylamine group is the same as the example of the alkyl group described above.

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 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, a stilbenyl group, and a styrenyl group, but are not limited thereto.

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

In the present specification, the 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 anthracenyl group, a phenanthryl group, a triphenyl group, a pyrenyl group, a phenalenyl group, a perylenyl group, a chrysenyl group, a fluorenyl group, and the like, but are limited thereto. no.

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 될 수 있다. 다만, 이에 한정되는 것은 아니다.When the fluorenyl group is substituted,

,

,

,

,

And

Can be, etc. However, it is not limited thereto.

In the present specification, examples of the arylamine group include a substituted or unsubstituted monoarylamine group, a substituted or unsubstituted diarylamine group, or a substituted or unsubstituted triarylamine group. The aryl group in the arylamine group may be a monocyclic aryl group or a polycyclic aryl group. The arylamine group including two or more aryl groups may include a monocyclic aryl group, a polycyclic aryl group, or a monocyclic aryl group and a polycyclic aryl group at the same time. For example, the aryl group in the arylamine group may be selected from the examples of the aryl group described above.

In the present specification, the aryl group in the aryloxy group, the N-arylalkylamine group, and the N-arylheteroarylamine 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.

In the present specification, the heteroaryl group includes one or more atoms other than carbon and one or more heteroatoms, 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 thiophene group, furanyl group, pyrrole group, imidazolyl group, thiazolyl group, oxazolyl group, oxadiazolyl group, pyridyl group, bipyridyl group, pyrimidyl group, triazinyl group, tria Zolyl group, acridyl group, pyridazinyl group, pyrazinyl group, quinolinyl group, quinazolinyl group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group , Isoquinolinyl group, indolyl group, carbazolyl group, benzoxazolyl group, benzimidazolyl group, benzocarbazolyl group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group ), an isoxazolyl group, a thiadiazolyl group, a benzothiazolyl group, a phenothiazinyl group, and a dibenzofuranyl group, but are not limited thereto.

In the present specification, examples of the heteroarylamine group include a substituted or unsubstituted monoheteroarylamine group, a substituted or unsubstituted diheteroarylamine group, or a substituted or unsubstituted triheteroarylamine 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, examples of the heteroaryl group in the N-arylheteroarylamine group and the N-alkylheteroarylamine group are the same as those of the aforementioned heteroaryl group.

According to an exemplary embodiment of the present specification, the acridine derivative represented by Formula 1 may be represented by any one of the compounds represented by Formulas 2 to 7.

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

In Formulas 2 to 7, R1 to R6, L1 to L3, Ar1, Ar2, and a to d are as defined in Formula 1.

According to an exemplary embodiment of the present specification, R1 and R2 are combined with each other.

According to an exemplary embodiment of the present specification, R3 to R6 are hydrogen.

According to an exemplary embodiment of the present specification, L1 to L3 are the same as or different from each other, and each independently a direct bond; Or a substituted or unsubstituted arylene group having 6 to 20 carbon atoms.

According to an exemplary embodiment of the present specification, L1 to L3 are the same as or different from each other, and each independently a direct bond; Or an arylene group unsubstituted or substituted with an alkyl group having 1 to 10 carbon atoms.

According to an exemplary embodiment of the present specification, L1 to L3 are the same as or different from each other, and each independently a direct bond; Phenylene group; Divalent naphthyl group; Divalent biphenyl group; Divalent terphenyl group; Divalent spirobifluorene group; Divalent triphenylene group; Divalent dimethylfluorene group; Or a divalent diphenylfluorene group.

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

According to the exemplary embodiment of the present specification, Ar1 and Ar2 are the same as or different from each other, and are each independently an aryl group having 6 to 20 carbon atoms substituted or unsubstituted with an alkyl group or an aryl group.

According to an exemplary embodiment of the present specification, Ar1 and Ar2 are the same as or different from each other, and are each independently an aryl group having 6 to 20 carbon atoms substituted or unsubstituted with an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms. .

According to an exemplary embodiment of the present specification, Ar1 and Ar2 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 pyrene group, a triphenylene group, a spirobifluorene group. , A phenanthrene group, or an anthracene group, and the aryl groups listed above are substituted with one or more substituents selected from the group consisting of deuterium, nitrile group, halogen group, alkyl group, aryl group, heteroaryl group, silyl group, and phosphine oxide group. Or unsubstituted.

According to the exemplary embodiment of the present specification, Ar1 and Ar2 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 pyrene group, a triphenylene group, a phenanthrene group, or It is an anthracene group, and the aryl groups listed above are unsubstituted or substituted with an alkyl group or an aryl group.

According to the exemplary embodiment of the present specification, Ar1 and Ar2 are the same as or different from each other, and each independently a phenyl group, naphthyl group, biphenyl group, terphenyl group, and 1 to 10 carbon atoms substituted or unsubstituted with an alkyl group having 1 to 10 carbon atoms. It is a fluorene group or a triphenylene group unsubstituted or substituted with an alkyl group of or an aryl group having 6 to 20 carbon atoms.

According to an exemplary embodiment of the present specification, Ar1 and Ar2 are the same as or different from each other, and each independently a heteroaryl group containing at least one of N, O, and S having 3 to 20 carbon atoms.

According to an exemplary embodiment of the present specification, Ar1 and Ar2 are the same as or different from each other, and each independently a monocyclic or polycyclic heteroaryl group containing at least one of N, O, and S having 3 to 20 carbon atoms.

According to an exemplary embodiment of the present specification, Ar1 and Ar2 are the same as or different from each other, and each independently a pyridine group, a pyrimidine group, a triazine group, a carbazole group, a thiophene group, a furan group, a benzothiophene group, and a benzo. It is a furan group, a dibenzothiophene group, or a dibenzofuran group.

According to an exemplary embodiment of the present specification, Ar1 and Ar2 are the same as or different from each other, and each independently a dibenzothiophene group or a dibenzofuran group.

According to an exemplary embodiment of the present specification, Ar1 and Ar2 are the same as or different from each other, and each independently an aryl group having 6 to 20 carbon atoms substituted or unsubstituted with an alkyl group having 1 to 10 carbon atoms; Or a heteroaryl group containing at least one of N, O, and S having 3 to 20 carbon atoms.

According to an exemplary embodiment of the present specification, Ar1 and Ar2 are the same as or different from each other, and each independently a phenyl group, biphenyl group, naphthyl group, terphenyl group, dimethylfluorene group, diphenylfluorene substituted or unsubstituted with a methyl group. Group, dibenzofuran group, or dibenzothiophene group.

According to another exemplary embodiment of the present specification, -(L1)N(L2-Ar1)(L3-Ar2), which is a combination of L1 to L3, Ar1 and Ar2, may be any one of the following substituents, but is limited thereto. It is not.

는 코어와 결합하는 부위이다.remind

Is the site that binds to the core.

According to another exemplary embodiment of the present specification, the compounds of Formulas 1 to 7 may be represented by the following structural formulas.

According to an exemplary embodiment of the present specification, the intermediate of the compound of Formulas 1 to 7 may be prepared according to the following reaction scheme, but is not limited thereto. In the following reaction scheme, various types of intermediates can be synthesized according to the type and number of substituents appropriately selecting a known starting material by a person skilled in the art. As for the reaction type and reaction conditions, those known in the art may be used.

When the preparation formulas described in the examples of the present specification and the intermediates are appropriately combined based on common technical knowledge, all of the compounds of Formulas 1 to 7 described in the present specification can be prepared.

According to an exemplary embodiment of the present specification, the first electrode; A second electrode provided opposite to the first electrode; And one or two or more organic material layers provided between the first electrode and the second electrode, wherein at least one of the organic material layers comprises the aforementioned acridine derivative. to provide.

According to an exemplary embodiment of the present specification, the organic material layer of the organic light emitting device of the present specification may be formed in a single-layer structure, but may be formed in a multilayer structure in which two or more organic material layers are stacked. For example, the organic light emitting device of the present invention may have a structure including a hole injection layer, a hole transport layer, an electron suppression layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, and the like as an organic material layer. However, the structure of the organic light-emitting device is not limited thereto, and may include fewer or more organic layers.

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 device in which a first electrode 2, a light emitting layer 3, and a second electrode 4 are sequentially stacked on a substrate 1. 1 is an exemplary structure of an organic light emitting device according to an exemplary embodiment of the present specification, and may further include another organic material layer.

2 shows a first electrode (2), a hole injection layer (5), a hole transport layer (6), a light emitting layer (3), an electron transport layer (7), an electron injection layer (8) and a second electrode ( 4) The structure of the organic light emitting device in which these 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.

3, a first electrode (2), a hole injection layer (5), a hole transport layer (6), an electron suppression layer (9), a light emitting layer (3), a hole suppression layer (10), an electron injection layer on the substrate (1), and A structure of an organic light-emitting device in which the transport layer 11 and the second electrode 4 are sequentially stacked is illustrated. 3 is an exemplary structure according to the exemplary embodiment of the present specification, and may further include another organic material layer.

According to an exemplary embodiment of the present specification, the organic material layer includes a hole injection layer, a hole transport layer, or an electron suppression layer, and the hole injection layer, a hole transport layer, or an electron suppression layer includes an acridine derivative represented by Formula 1 above. do.

According to an exemplary embodiment of the present specification, the organic material layer includes an electron-suppression layer, and the electron-suppression layer includes an acridine derivative represented by Formula 1 above.

According to an exemplary embodiment of the present specification, the organic material layer includes an electron injection layer, an electron transport layer, or a hole suppression layer, and the electron injection layer, the electron transport layer, or the hole suppression layer includes an acridine derivative represented by Formula 1 above. do.

According to an exemplary embodiment of the present specification, the organic material layer includes an emission layer, and the emission layer includes an acridine derivative represented by Formula 1 above.

According to the exemplary embodiment of the present specification, the organic material layer may further include one or more layers selected from the group consisting of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer.

The organic light-emitting device of the present specification is made of materials and methods known in the art, except that at least one of the organic material layers contains an acridine derivative of the present specification, that is, an acridine derivative represented by Formula 1 above. Can be manufactured.

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

For example, the organic light emitting device of the present 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 this 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. 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 anode 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 as a hole injection material, and has an 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 generated in the light-emitting layer to the electron injection layer or the electron injection material and has excellent thin film formation ability is preferable. It is preferable that the HOMO (highest occupied molecular orbital) of the hole injection material is between the work function of the positive electrode material and the HOMO of the surrounding organic material layer. Specific examples of hole injection materials include metal porphyrin, oligothiophene, arylamine-based organic substances, hexanitrile hexaazatriphenylene-based organic substances, quinacridone-based organic substances, and perylene-based organic substances. Organic substances, anthraquinone, polyaniline, and polythiophene-based conductive polymers, but are not limited thereto.

The hole transport layer is a layer that receives holes from the hole injection layer and transports holes to the emission layer.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.

As the light-emitting material of the light-emitting layer, a material capable of emitting light in the visible light region by transporting and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, and a material having good quantum efficiency against fluorescence or phosphorescence is preferable. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq ₃ ); Carbazole-based compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzoquinoline-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 emission layer may include a host material and a dopant material. The host material includes a condensed aromatic ring derivative or a hetero ring-containing compound. 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.

Examples of the dopant material include aromatic amine derivatives, strylamine compounds, boron complexes, fluoranthene compounds, and metal complexes. Specifically, the aromatic amine derivative is a condensed aromatic ring derivative having a substituted or unsubstituted arylamino group, and includes pyrene, anthracene, chrysene, periflanthene and the like having an arylamino group, and the styrylamine compound is substituted or unsubstituted As a compound in which at least one arylvinyl group is substituted on the arylamine, one or two or more substituents selected from the group consisting of aryl group, silyl group, alkyl group, cycloalkyl group and arylamino group are substituted or unsubstituted. Specifically, there are styrylamine, styryldiamine, styryltriamine, and styryltetraamine, but are not limited thereto. In addition, examples of the metal complex include, but are not limited to, an iridium complex and a platinum complex.

The electron transport material of the electron transport layer is a layer that receives electrons from the electron injection layer and transports electrons to the emission layer. The electron transport material is a material that can receive electrons from the cathode and transfer them to the emission layer. This large material is suitable. Specific examples include 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 the light emitting material, and injects holes of excitons generated from the light emitting layer. A compound that prevents migration to the layer and is excellent in thin film forming 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 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)( 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.

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.

Manufacturing example One

Compound A (6.50 g, 14.74 mmol) and compound a1 (7.48 g, 16.95 mmol) were completely dissolved in 240 mL of tetrahydrofuran in a 500 mL round bottom flask in a nitrogen atmosphere, and then 2M aqueous potassium carbonate solution (120 mL) was added. , Tetrakis-(triphenylphosphine)palladium (0.51 g, 0.44 mmol) was added, followed by heating and stirring for 3 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 210 mL of ethyl acetate to prepare compound 1 (9.78 g, 83%).

MS[M+H] ⁺ = 803

Manufacturing example 2

Compound A (5.50 g, 12.47 mmol) and compound a2 (6.90 g, 14.34 mmol) were completely dissolved in 220 mL of tetrahydrofuran in a 500 mL round bottom flask in a nitrogen atmosphere, and then 2M aqueous potassium carbonate solution (110 mL) was added. , Tetrakis-(triphenylphosphine)palladium (0.43 g, 0.37 mmol) was added, followed by heating and stirring for 2 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 160 mL of ethyl acetate to prepare compound 2 (7.12 g, 68%).

MS[M+H] ⁺ = 843

Manufacturing example 3

Compound A (4.50g, 10.20mmol) and compound a3 (6.23 g, 11.73 mmol) were completely dissolved in 240 mL of tetrahydrofuran in a 500 mL round-bottom flask in a nitrogen atmosphere, and then 2M aqueous potassium carbonate solution (120 mL) was added. , Tetrakis-(triphenylphosphine)palladium (0.35 g, 0.31 mmol) was added, followed by heating and stirring for 3 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 250 mL of tetrahydrofuran to prepare compound 3 (6.95 g, 76%).

MS[M+H] ⁺ = 893

Manufacturing example 4

Compound A (5.0 g, 11.34 mmol) and compound a4 (5.75 g, 13.04 mmol) were completely dissolved in 160 mL of tetrahydrofuran in a 500 mL round-bottom flask in a nitrogen atmosphere, and then 2M aqueous potassium carbonate solution (80 mL) was added. , Tetrakis-(triphenylphosphine)palladium (0.39 g, 0.34 mmol) was added, followed by heating and stirring for 5 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 210 mL of ethyl acetate to prepare compound 4 (4.69 g, 52%).

MS[M+H] ⁺ = 803

Manufacturing example 5

Compound A (6.50 g, 14.74 mmol) and compound a5 (5.44 g, 16.95 mmol) were completely dissolved in 220 mL of xylene in a 500 mL round-bottom flask in a nitrogen atmosphere, and NaOtBu (2.27 g, 23.58 mmol) was added, and After adding bis (tri-ter-butylphosphine) palladium (0) (0.15 g, 0.29 mmol), the mixture was heated and stirred for 3 hours. After lowering the temperature to room temperature and filtering to remove the base, xylene was concentrated under reduced pressure and recrystallized with 210 mL of ethyl acetate to prepare compound 5 (8.61 g, yield: 80%).

MS[M+H] ⁺ = 727

Manufacturing example 6

Compound A (6.50 g, 14.74 mmol) and compound a6 (6.12 g, 16.95 mmol) were completely dissolved in 200 mL of xylene in a 500 mL round bottom flask in a nitrogen atmosphere, and NaOtBu (2.27 g, 23.58 mmol) was added, and After adding bis (tri-ter-butylphosphine) palladium (0) (0.15 g, 0.29 mmol), the mixture was heated and stirred for 2 hours. After lowering the temperature to room temperature and filtering to remove the base, xylene was concentrated under reduced pressure and recrystallized with 220 mL of ethyl acetate to prepare compound 6 (6.67 g, yield: 59%).

MS[M+H] ⁺ = 767

Manufacturing example 7

Compound A (5.50 g, 12.47 mmol) and compound a7 (4.60 g, 14.34 mmol) were completely dissolved in 160 mL of xylene in a 500 mL round-bottom flask in a nitrogen atmosphere, and NaOtBu (1.92 g, 19.95 mmol) was added, and After adding bis (tri-ter-butylphosphine) palladium (0) (0.13 g, 0.25 mmol), the mixture was heated and stirred for 4 hours. After lowering the temperature to room temperature and filtering to remove the base, xylene was concentrated under reduced pressure and recrystallized with 230 mL of ethyl acetate to prepare compound 7 (7.12 g, yield: 79%).

MS[M+H] ⁺ = 727

Manufacturing example 8

Compound A (3.50 g, 7.94 mmol) and compound a8 (3.66 g, 9.13 mmol) were completely dissolved in 150 mL of xylene in a 500 mL round bottom flask in a nitrogen atmosphere, and NaOtBu (1.22 g, 12.70 mmol) was added, and After adding bis (tri-ter-butylphosphine) palladium (0) (0.08 g, 0.16 mmol), the mixture was heated and stirred for 1 hour. After lowering the temperature to room temperature and filtering to remove the base, xylene was concentrated under reduced pressure and recrystallized with 210 mL of ethyl acetate to prepare compound 8 (3.45 g, yield: 54%).

MS[M+H] ⁺ = 807

Manufacturing example 9

Compound B (5.50 g, 12.47 mmol) and compound a9 (6.33 g, 14.34 mmol) were completely dissolved in 210 mL of tetrahydrofuran in a 500 mL round-bottom flask in a nitrogen atmosphere, and then 2M aqueous potassium carbonate solution (100 mL) was added. , Tetrakis-(triphenylphosphine)palladium (0.43 g, 0.37 mmol) was added, followed by heating and stirring for 4 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 350 mL of ethyl acetate to prepare compound 9 (8.86 g, 88%).

MS[M+H] ⁺ = 803

Manufacturing example 10

Compound B (4.50 g, 10.20 mmol) and compound a10 (3.77 g, 11.73 mmol) were completely dissolved in 160 mL of xylene in a 500 mL round bottom flask in a nitrogen atmosphere, and NaOtBu (1.57 g, 16.33 mmol) was added, and After adding bis (tri-ter-butylphosphine) palladium (0) (0.10 g, 0.20 mmol), the mixture was heated and stirred for 2 hours. After lowering the temperature to room temperature and filtering to remove the base, xylene was concentrated under reduced pressure and recrystallized with 180 mL of ethyl acetate to prepare compound 10 (5.56 g, yield: 75%).

MS[M+H] ⁺ = 727

Manufacturing example 11

Compound C (5.0 g, 11.34 mmol) and compound a11 (5.10 g, 13.04 mmol) were completely dissolved in 160 mL of xylene in a 500 mL round-bottom flask in a nitrogen atmosphere, and NaOtBu (1.74 g, 18.14 mmol) was added, and After adding bis (tri-ter-butylphosphine) palladium (0) (0.12 g, 0.23 mmol), the mixture was heated and stirred for 3 hours. After lowering the temperature to room temperature and filtering to remove the base, xylene was concentrated under reduced pressure and recrystallized with 210 mL of ethyl acetate to prepare compound 11 (6.23 g, yield: 69%).

MS[M+H] ⁺ = 797

Example 1-1

A glass substrate coated with a thin film of ITO (indium tin oxide) having a thickness of 1,000Å was put in distilled water dissolved in a detergent and washed with ultrasonic waves. At this time, a Fischer Co. product was used as a detergent, and distilled water secondarily filtered by a filter (filtration) manufactured by Millipore Co. was used as distilled water. After washing the ITO for 30 minutes, it was repeated twice with distilled water to perform ultrasonic cleaning for 10 minutes. After washing with distilled water, ultrasonic washing was performed with a solvent of isopropyl alcohol, acetone, and methanol, dried, and then transported to a plasma cleaner. In addition, after cleaning the substrate for 5 minutes using oxygen plasma, the substrate was transported to a vacuum evaporator.

On the thus prepared ITO transparent electrode, a compound represented by the following formula HAT was thermally vacuum deposited to a thickness of 100 Å to form a hole injection layer. A hole transport layer was formed by vacuum depositing a compound (1250Å) represented by the following formula HT1 on the hole injection layer. Subsequently, the compound of Preparation Example 1 prepared above with a film thickness of 150 Å was vacuum deposited on the hole transport layer to form an electron suppressing layer. Subsequently, a light emitting layer was formed by vacuum depositing a compound represented by the following formula BH and a compound represented by the following formula BD with a film thickness of 200 Å on the electron suppressing layer at a weight ratio of 25:1. A hole blocking layer was formed by vacuum depositing a compound represented by the following Chemical Formula HB1 with a film thickness of 50 Å on the emission layer. Subsequently, a compound represented by the following formula ET1 and a compound represented by the following formula LiQ were vacuum-deposited at a weight ratio of 1:1 on the hole blocking layer to form an electron injection and transport layer with a thickness of 310Å. Lithium fluoride (LiF) in a thickness of 12 Å and aluminum in a thickness of 1,000 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 ~ 0.7Å/sec, the deposition rate of lithium fluoride at the cathode was 0.3Å/sec, and the deposition rate of aluminum was 2Å/sec, and the vacuum degree during deposition was 2x10 ^-7 ~ An organic light emitting device was manufactured by maintaining ^{5x10 -6 torr.}

Example 1-2 to Example 1-11

An organic light-emitting device was manufactured in the same manner as in Example 1-1, except that the compound shown in Table 1 was used instead of the compound of Preparation Example 1.

Comparative example 1-1 to 1-3

An organic light-emitting device was manufactured in the same manner as in Example 1-1, except that the compound shown in Table 1 was used instead of the compound of Preparation Example 1. The compounds of EB1, EB2, and EB3 used in Table 1 are as follows.

Experimental example One

When a current was applied to the organic light emitting device prepared in the above Examples and Comparative Examples, voltage, efficiency, color coordinates, and lifetime were measured, and the results are shown in Table 1 below. T95 refers to the time it takes for the luminance to decrease from the initial luminance (1600 nit) to 95%.

compound
(Electronic suppression layer) Voltage
(V@10mA
/cm ² ) efficiency
(cd/A@10mA
/cm ² ) Color coordinates
(x,y) T95
(hr) Example 1-1 Manufacturing Example 1 4.51 6.30 (0.140, 0.045) 275 Example 1-2 Manufacturing Example 2 4.33 6.46 (0.141, 0.047) 310 Example 1-3 Manufacturing Example 3 4.56 6.34 (0.143, 0.047) 295 Example 1-4 Manufacturing Example 4 4.41 6.42 (0.139, 0.043) 285 Example 1-5 Manufacturing Example 5 4.50 6.33 (0.140, 0.047) 275 Example 1-6 Manufacturing Example 6 4.73 6.15 (0.141, 0.046) 310 Example 1-7 Manufacturing Example 7 4.64 6.29 (0.140, 0.044) 290 Example 1-8 Manufacturing Example 8 4.46 6.44 (0.141, 0.046) 260 Example 1-9 Manufacturing Example 9 4.41 6.42 (0.138, 0.044) 280 Example 1-10 Manufacturing Example 10 4.50 6.33 (0.139, 0.043) 295 Example 1-11 Manufacturing Example 11 4.43 6.41 (0.140, 0.043) 285 Comparative Example 1-1 EB1 5.67 5.01 (0.139, 0.043) 125 Comparative Example 1-2 EB2 5.12 5.75 (0.142, 0.045) 165 Comparative Example 1-3 EB3 7.25 3.16 (0.150, 0.049) 20

As shown in Table 1, the organic light-emitting device using the compound of the present invention as an electron suppressing layer exhibited excellent characteristics in terms of efficiency, driving voltage, and stability of the organic light-emitting device. Compared to the organic light emitting device manufactured by using the compound of EB2 substituted with amine groups on both sides of the phenyl at position 9 of the core dihydroacridine of the present invention and EB3 substituted with two amine groups on one side as an electron suppressing layer, It showed the characteristics of long life. In particular, the reason for the large increase in voltage is that the HOMO value increases as the amine groups are located on both sides, and the barrier with the light-emitting layer increases. In addition, the organic light-emitting device manufactured by using the compound of EB3 in which phosphine oxide is substituted for the amine group in the phenyl group of No. 9 as the electron suppressing layer showed a result that the lifespan characteristics were significantly deteriorated. In general, it was confirmed that if there is no amine group as a substituent, it cannot be applied as a hole transport layer and an electron suppression layer.

As shown in the results of Table 1, it was confirmed that the compound according to the present invention has excellent electron blocking ability and thus can be applied to an organic light-emitting device.

Although the preferred embodiment (electron suppression layer) of the present invention has been described above, the present invention is not limited thereto, and various modifications can be made within the scope of the claims and the detailed description of the invention. It belongs to the scope of the invention.

1: substrate
2: first electrode
3: light-emitting layer
4: second electrode
5: hole injection layer
6: hole transport layer
7: electron transport layer
8: electron injection layer
9: electron suppression layer
10: hole suppression layer
11: Electron injection and transport layer

Claims (7)

An acridine derivative represented by the following formula (1):
[Formula 1]

In Formula 1,
R1 and R2 are bonded to each other,
R3 to R6 are each hydrogen,
L1 to L3 are the same as or different from each other, and each independently a direct bond; Or a phenylene group,
Ar1 is a fluorenyl group unsubstituted or substituted with an alkyl group having 1 to 10 carbon atoms; Dibenzothiophene group; Or a dibenzofuran group,
Ar2 is a phenyl group; Biphenyl group; Terphenyl group; Or a naphthyl group,
a is an integer from 0 to 4,
b is an integer from 0 to 7,
c is an integer from 0 to 5,
d is an integer from 0 to 4. The method of claim 1, wherein the formula 1 is an acridine derivative represented by any one of the following formulas 5 to 7:
[Formula 5]

[Formula 6]

[Formula 7]

In Formulas 5 to 7, R3 to R6, L1 to L3, Ar1, Ar2, and a to d are as defined in claim 1 above. delete The acridine derivative of claim 1, wherein the combination of L1 to L3, Ar1 and Ar2 is any one of the following structures:

. An acridine derivative that is any one selected from the following compounds:

. A first electrode; A second electrode provided opposite to the first electrode; And one or two or more organic material layers provided between the first electrode and the second electrode, wherein at least one of the organic material layers is acridin according to any one of claims 1, 2, 4, and 5. Organic light-emitting device comprising a derivative. The organic light-emitting device of claim 6, wherein the organic material layer includes a hole injection layer, a hole transport layer, or an electron suppression layer, and the hole injection layer, a hole transport layer, or an electron suppression layer includes the acridine derivative.

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