KR102109075B1 - Organic light emitting device - Google Patents

Abstract

The present invention provides an organic light emitting device with improved driving voltage, efficiency, and lifetime.

Description

Organic light emitting device {Organic light emitting device}

The present invention relates to an organic light emitting device with improved driving voltage, efficiency, and life.

In general, the organic light emitting phenomenon refers to a phenomenon that converts electrical energy into light energy using an organic material. The organic light emitting device using the organic light emitting phenomenon has a wide viewing angle, excellent contrast, and a fast response time, and has excellent luminance, driving voltage, and response speed characteristics, and thus many studies have been conducted.

The organic light emitting device generally has a structure including an anode and a cathode and an organic material layer between the anode and the cathode. In order to increase the efficiency and stability of the organic light emitting device, the organic material layer is often formed of a multi-layered structure composed of different materials, and may be formed of, 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. When a voltage is applied between two electrodes in the structure of the organic light emitting device, holes are injected at the anode, and electrons are injected at the cathode, and an exciton is formed when the injected holes meet the electrons. When it falls to the ground again, it glows.

In the organic light emitting device as described above, development of an organic light emitting device with improved driving voltage, efficiency, and lifetime is continuously required.

Korean Patent Publication No. 10-2000-0051826

The present invention relates to an organic light emitting device with improved driving voltage, efficiency, and life.

The present invention provides the following organic light emitting device:

anode,

cathode,

A light emitting layer between the anode and the cathode, and

An electron suppressing layer between the anode and the light emitting layer,

The electron suppressing layer includes a compound represented by Formula 1 below,

The light emitting layer includes a compound represented by the formula (2),

Organic light emitting device:

[Formula 1]

In Chemical Formula 1,

Ar ₁ and Ar ₂ are each independently substituted or unsubstituted C _6-18 aryl; Or C _2-60 heteroarylene containing one or more heteroatoms selected from the group consisting of substituted or unsubstituted O and S,

L ₁ , L ₂ , and L ₃ are each independently bonded; Substituted or unsubstituted C _6-60 arylene; Or C _2-60 heteroarylene containing one or more heteroatoms selected from the group consisting of substituted or unsubstituted O, N, Si and S,

[Formula 2]

In Chemical Formula 2,

Ar ₃ and Ar ₄ are each independently substituted or unsubstituted C _6-60 aryl; Or C _2-60 heteroarylene containing one or more heteroatoms selected from the group consisting of substituted or unsubstituted O, N, Si and S,

L ₄ and L ₅ are each independently bonded; Substituted or unsubstituted C _6-60 arylene; Or C _2-60 heteroarylene containing one or more heteroatoms selected from the group consisting of substituted or unsubstituted O, N, Si and S.

The organic light-emitting device described above is excellent in driving voltage, efficiency, and life.

1 is an example of an organic light emitting device comprising a substrate 1, an anode 2, a hole transport layer 3, an electron suppressing layer 4, a light emitting layer 5, an electron transport layer 6, and a cathode 7 It is shown.
2 shows a substrate 1, an anode 2, a hole injection layer 8, a hole transport layer 3, an electron suppressing layer 4, a light emitting layer 5, an electron transport layer 6, and a cathode 6 It shows an example of an organic light emitting device consisting of.

Hereinafter, it will be described in more detail in order to help the understanding of the present invention.

는 다른 치환기에 연결되는 결합을 의미한다. In this specification,

Means a linkage to another substituent.

The term "substituted or unsubstituted" as used herein refers to deuterium; Halogen group; Nitrile group; Nitro group; Hydroxy group; Carbonyl group; Ester groups; Imide group; Amino group; Phosphine oxide group; Alkoxy groups; Aryloxy group; Alkyl thioxy group; Arylthioxy group; Alkyl sulfoxy group; Aryl sulfoxyl group; Silyl group; Boron group; Alkyl groups; Cycloalkyl group; Alkenyl group; Aryl group; Aralkyl group; Ar alkenyl group; Alkyl aryl groups; Alkylamine groups; Aralkylamine group; Heteroarylamine group; Arylamine group; Arylphosphine group; Or substituted or unsubstituted with one or more substituents selected from the group consisting of heterocyclic groups containing one or more of N, O and S atoms, or substituted or unsubstituted with two or more substituents among the exemplified substituents above . For example, "a substituent having two or more substituents" may be a biphenyl group. That is, the biphenyl group may be an aryl group or may be interpreted as a substituent to which two phenyl groups are connected.

In this specification, the number of carbon atoms of the carbonyl group is not particularly limited, but is preferably 1 to 40 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.

In the present specification, the oxygen of the ester group may be substituted with a straight chain, branched or cyclic alkyl group having 1 to 25 carbon atoms or an aryl group having 6 to 25 carbon atoms. Specifically, it may be a compound of the following structural formula, but is not limited thereto.

In this specification, the number of carbon atoms of the imide group is not particularly limited, but is preferably 1 to 25 carbon atoms. Specifically, it may be a compound having the following structure, but is 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 boron group is specifically a trimethyl boron group, a triethyl boron group, a t-butyl dimethyl boron group, a triphenyl boron group, a phenyl boron group, and the like, but is not limited thereto.

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

In the present specification, the alkyl group may be straight chain or branched chain, and carbon number is not particularly limited, but is preferably 1 to 40. According to an exemplary embodiment, the alkyl group has 1 to 20 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 10 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 6 carbon atoms. Specific examples of the alkyl group are 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 -Dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, and the like, but is not limited thereto.

In the present specification, the alkenyl group may be a straight chain or a branched chain, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to one embodiment, the carbon number of the alkenyl group is 2 to 20. According to another exemplary embodiment, the alkenyl group has 2 to 10 carbon atoms. According to another exemplary embodiment, the alkenyl group has 2 to 6 carbon atoms. 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, styrenyl group, styrenyl group, and the like, but are not limited thereto.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and according to an exemplary embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another exemplary embodiment, the cycloalkyl group has 3 to 20 carbon atoms. According to another exemplary embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specifically, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3, 4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like, but is not limited thereto.

In the present specification, the aryl group is not particularly limited, but is preferably 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the carbon number of the aryl group is 6 to 30. According to one embodiment, the carbon number of the aryl group is 6 to 20. The aryl group may be a phenyl group, a biphenyl group, a terphenyl group, etc., as a monocyclic aryl group, but is not limited thereto. The polycyclic aryl group may be a naphthyl group, anthracenyl group, phenanthryl group, pyrenyl group, perylenyl group, chrysenyl group, fluorenyl group, and the like, but is not limited thereto.

등이 될 수 있다. 다만, 이에 한정되는 것은 아니다.In the present specification, the fluorenyl group may be substituted, and two substituents may combine with each other to form a spiro structure. When the fluorenyl group is substituted,

It can be back. However, it is not limited thereto.

In the present specification, the heterocyclic group is a heterocyclic group containing one or more of O, N, Si and S as heterogeneous elements, and the number of carbon atoms is not particularly limited, but is preferably 2 to 60 carbon atoms. Examples of the heterocyclic group include thiophene group, furan group, pyrrol group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, pyrimidyl group, triazine group, triazole group, Acridil group, pyridazine group, pyrazinyl group, quinolinyl group, quinazolinyl group, quinoxalinyl group, phthalazinyl group, pyridopyrimidinyl group, pyridopyrazinyl group, pyrazino pyrazinyl group, isoquinoline group , Indole group, carbazole group, benzoxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group, thiazolyl group, Isooxazolyl groups, oxadiazolyl groups, thiadiazolyl groups, benzothiazolyl groups, phenothiazinyl groups, and dibenzofuranyl groups, but are not limited thereto.

In the present specification, an aryl group in an aralkyl group, an alkenyl group, an alkylaryl group, and an arylamine group is the same as the exemplified aryl group described above. In the present specification, the alkyl group among the aralkyl group, alkylaryl group, and alkylamine group is the same as the above-described example of the alkyl group. In the present specification, heteroarylamine among heteroarylamines may be applied to the description of the aforementioned heterocyclic group. In the present specification, the alkenyl group in the alkenyl group is the same as the exemplified alkenyl group. In the present specification, the description of the aryl group described above may be applied, except that the arylene is a divalent group. In the present specification, the description of the heterocyclic group described above may be applied, except that the heteroarylene is a divalent group. In the present specification, the hydrocarbon ring is not a monovalent group, and the description of the aryl group or cycloalkyl group described above may be applied, except that two substituents are formed by bonding. In this specification, the heterocycle is not a monovalent group, and the description of the aforementioned heterocyclic group may be applied, except that two substituents are formed by bonding.

Hereinafter, the present invention will be described in detail for each configuration.

Anode and cathode

The positive electrode and the negative electrode used in the present invention mean electrodes used in organic light emitting devices.

The positive electrode material is preferably a material having a large work function so that hole injection into the organic material layer is smooth. Specific examples of the positive electrode material 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); Metal and oxide combinations such as ZnO: Al or SNO ₂ : Sb; Conductive polymers such as poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDOT), polypyrrole, and polyaniline, but are not limited thereto.

The cathode material is preferably 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 is a multilayer structure material such as LiF / Al or LiO ₂ / Al, but is not limited thereto.

Electronic suppression layer

The organic light emitting device according to the present invention includes an electron suppressing layer between the anode and the light emitting layer.

The electron suppressing layer serves to improve the efficiency of the organic light emitting device by suppressing electrons injected from the cathode from being transferred to the anode without recombination in the light emitting layer. In the present invention, a compound represented by Chemical Formula 1 is used as a material constituting the electron suppressing layer.

In Chemical Formula 1, preferably, Ar ₁ and Ar ₂ are each independently phenyl, biphenyline, terphenyline, naphthyl, phenanthrenyl, triphenylenyl, dimethylfluorenyl, diphenylfluorenyl, Spirobifluorenyl, dibenzofuranyl, or dibenzothiophenyl. Also preferably, is excluded from the definition of Ar ₁ and Ar _2, the Ar ₁ and Ar ₂ are both phenyl, or biphenyl Lin.

Further, preferably, L ₁ , L ₂ , and L ₃ are each independently a bond, phenylene, biphenylylene, naphthylene, or dimethylfluorenylene.

Representative examples of the compound represented by Formula 1 are as follows:

In addition, the compound represented by the formula (1) may be prepared as shown in the following scheme 1-1 or 1-2, the production method may be more specific in the production examples to be described later. In addition, the following Reaction Scheme 1-1 means the case where L1 is a bond in Formula 1.

[Scheme 1-1]

[Scheme 1-2]

(In Reaction Schemes 1-1 and 1-2, Ar ₁ , Ar ₂ , L ₁ , L ₂ and L ₃ are as defined above)

Emitting layer

The light emitting layer used in the present invention is a layer capable of emitting light in the visible light region by combining holes and electrons received from the anode and the cathode, and a material having good quantum efficiency for fluorescence or phosphorescence is preferable.

In general, the light emitting layer includes a host material and a dopant material, and in the present invention, the compound represented by Chemical Formula 2 is included as a host.

In Chemical Formula 2, preferably, Ar ₃ and Ar ₄ are each independently phenyl, biphenyline, terphenyline, naphthyl, phenanthrenyl, triphenylenyl, dimethylfluorenyl, or diphenylfluorenyl to be.

Also preferably, L ₄ and L ₅ are each independently a bond, phenylene, naphthylene, or anthracenylene.

Representative examples of the compound represented by Formula 2 are as follows:

In addition, the compound represented by the formula (2) can be prepared as shown in Scheme 2, the production method may be more specific in the production example to be described later.

[Scheme 2]

(In Reaction Scheme 2, Ar ₃ , Ar ₄ , L ₄ and L ₅ are as defined above)

The dopant material is not particularly limited as long as it is a material used in an organic light emitting device. Examples include aromatic amine derivatives, strylamine compounds, boron complexes, fluoranthene compounds, metal complexes, and the like. Specifically, the aromatic amine derivative is a condensed aromatic ring derivative having a substituted or unsubstituted arylamino group, and includes pyrene, anthracene, chrysene, periplanene, etc. having an arylamino group, and substituted or unsubstituted as a styrylamine compound. A compound in which at least one arylvinyl group is substituted with the arylamine, a substituent selected from 1 or 2 or more from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group, and an arylamino group is substituted or unsubstituted. Specifically, styrylamine, styryldiamine, styryltriamine, styryltetraamine, and the like, but are not limited thereto. Further, examples of the metal complex include an iridium complex, a platinum complex, and the like, but are not limited thereto.

Hole transport layer

The organic light emitting device according to the present invention may include a hole transport layer between the electron suppressing layer and the anode.

The hole transport layer is a layer that receives holes from the hole injection layer and transports holes from the hole injection layer to the light-emitting layer. It is a material that transports holes from the anode or the hole injection layer as a hole transport material and transfers them to the light emitting layer. This is suitable.

Specific examples of the hole transport material include an arylamine-based organic material, a conductive polymer, and a block copolymer having a conjugated portion and a non-conjugated portion, but are not limited thereto.

Hole injection layer  or Charge generating layer

The organic light emitting device according to the present invention may include a hole injection layer or a charge generating layer between the anode and the electron suppressing layer, or the anode and the hole transport layer.

The hole injection layer or the charge generating layer has the ability to transport holes and has a hole injection effect at the anode, an excellent hole injection effect for the light emitting layer or the light emitting material, and the electron injection layer or the electron injection material of the exciton generated in the light emitting layer It serves to prevent movement.

In particular, it is preferable that the hole injection layer or the charge generating layer contains a compound represented by the following formula (3):

[Formula 3]

In Chemical Formula 3,

R ₁ is any one selected from the group consisting of,

R ₂ is hydrogen, deuterium, halogen, cyano, or substituted or unsubstituted C _1-60 haloalkyl,

Ar ₅ is substituted or unsubstituted C _6-60 aryl; Or C _2-60 heteroarylene containing one or more heteroatoms selected from the group consisting of substituted or unsubstituted O, N, Si and S.

The compound represented by Chemical Formula 3 has excellent thermal stability and crystallization does not occur when manufacturing an organic light emitting device due to a three-dimensional structure according to a chemical structure, and also has high electron acceptability to lower the driving voltage of the organic light emitting device and enable long life. have.

In Formula 3, preferably, R ₂ is hydrogen, fluoro, trifluoromethyl.

Also preferably, Ar ₅ is phenyl, naphthyl, pyridine, quinazolinyl, or thiophenyl, wherein Ar ₅ is unsubstituted or halogen, C _1-6 haloalkyl, C _1-6 haloalkoxy, and cyan It is substituted with 1 to 5 substituents selected from the group consisting of furnaces. More preferably, the substituent is OCF ₃ , OCHF ₂ , OCH ₂ CF ₃ , OCH (CF ₃ ) ₂ , F, CF ₃ , or CN.

Representative examples of the compound represented by Formula 3 are as follows:

In addition, the compound represented by the formula (3) may be prepared as shown in the following scheme 3-1 or 3-2, and the production method may be more specific in the production examples to be described later.

[Scheme 3-1]

[Scheme 3-2]

(In the above reaction schemes 3-1 and 3-2, R ₁ , R ₂ and Ar ₅ are as defined above)

Electron transport layer  or Hole suppression layer

The organic light emitting device according to the present invention may include an electron transport layer or a hole suppressing layer between the light emitting layer and the cathode.

The electron transport layer or hole inhibiting layer is a layer that receives electrons from the electron injection layer formed on the cathode or the cathode to transport electrons to the light emitting layer, and also suppresses the transport of holes from the light emitting layer. As a material capable of receiving electrons well and transferring them to the light emitting layer, a material having high mobility for electrons is suitable.

It is preferable that the electron transport layer or the hole inhibiting layer include a compound represented by the following Chemical Formula 4 or a compound represented by the following Chemical Formula 5:

[Formula 4]

In Chemical Formula 4,

L ₆ and L ₇ are each independently a bond; Or substituted or unsubstituted C _6-60 arylene,

Ar ₆ and Ar ₇ are each independently substituted or unsubstituted C _6-60 aryl; Or C _2-60 heteroaryl containing one or more heteroatoms selected from the group consisting of substituted or unsubstituted O, N, Si and S,

[Formula 5]

In Chemical Formula 5,

X ₁ to X ₃ are each independently N, or CH,

L ₈ and L ₉ are each independently a bond; Or substituted or unsubstituted C _6-60 arylene,

Ar ₈ and Ar ₉ are each independently substituted or unsubstituted C _6-60 aryl; Or C _2-60 heteroaryl containing one or more heteroatoms selected from the group consisting of substituted or unsubstituted O, N, Si and S,

n is an integer from 1 to 5.

In Chemical Formula 4, preferably, L ₆ and L ₇ are each independently a bond, phenylene, or biphenylylene.

Also preferably, Ar ₆ and Ar ₇ are each independently phenyl, biphenyline, terphenyline, naphthyl, dimethylfluorenyl, or pyridinyl.

Representative examples of the compound represented by Formula 4 are as follows:

In addition, the compound represented by the formula (4) can be prepared as shown in the following scheme 4-1 or 4-2, the production method may be more specific in the production example to be described later. In addition, the following Reaction Scheme 4-1 means that L ₄ in Formula ₄ is a bond.

[Scheme 4-1]

[Scheme 4-2]

(In Reaction Schemes 4-1 and 4-2, L ₆ , L ₇ , Ar ₆ , and Ar ₇ are as defined above)

In Chemical Formula 5, preferably, at least one of X ₁ to X ₃ is N.

Also preferably, L ₈ and L ₉ are each independently phenylene.

Further, preferably, Ar ₈ and Ar ₉ are each independently phenyl, biphenyl, or dimethylfluorenyl.

Representative examples of the compound represented by Formula 5 are as follows:

In addition, the compound represented by the formula (5) can be prepared as shown in Scheme 5, the production method may be more specific in the production examples to be described later.

[Scheme 5]

(In Reaction Scheme 5, X ₁ to X ₃ , L ₈ , L ₉ , Ar ₈ , Ar ₉ and n are as defined above)

Electron injection layer

The organic light emitting device according to the present invention may further include an electron injection layer between the electron transport layer and the cathode. The electron injection layer is a layer that injects electrons from an electrode, has the ability to transport electrons, has an electron injection effect from a cathode, an excellent electron injection effect for a light emitting layer or a light emitting material, and injects holes generated in the light emitting layer A compound that prevents migration to the layer and has excellent thin film forming ability is preferred.

Specific examples of the material that can be used as the electron injection layer, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preolee Nilidene methane, anthrone, and the like, and derivatives thereof, metal 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) ( There are o-cresolato) gallium, bis (2-methyl-8-quinolinato) (1-naphtolato) aluminum, bis (2-methyl-8-quinolinato) (2-naphtholato) gallium, It is not limited to this.

Organic light emitting diode

The structure of the organic light emitting device according to the present invention is illustrated in the drawings. 1 is an example of an organic light emitting device comprising a substrate 1, an anode 2, a hole transport layer 3, an electron suppressing layer 4, a light emitting layer 5, an electron transport layer 6, and a cathode 7 It is shown. 2, the substrate 1, the anode 2, the hole injection layer 8, the hole transport layer 3, the electron suppressing layer 4, the light emitting layer 5, the electron transport layer 6, and the cathode ( 6) shows an example of an organic light emitting device.

The organic light emitting device according to the present invention can be manufactured by sequentially stacking the above-described configuration. At this time, a positive electrode is formed by depositing a metal or conductive metal oxide or an alloy thereof on a substrate using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation. And, after forming the above-described each layer on it, it can be prepared by depositing a material that can be used as a cathode thereon. In addition to this method, an organic light emitting device may be formed by sequentially depositing a cathode material, an organic material layer, and a cathode material on a substrate. In addition, the light emitting layer may be formed by a host and a dopant by a vacuum deposition method as well as a solution application method. Here, the solution application method means spin coating, dip coating, doctor blading, inkjet printing, screen printing, spraying, roll coating, and the like, but is not limited to these.

In addition to this method, an organic light emitting device may be manufactured by sequentially depositing an organic material layer and a cathode material from a cathode material on a substrate (WO 2003/012890). However, the manufacturing method is not limited thereto.

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

Hereinafter, preferred embodiments are provided to help understanding of the present invention. However, the following examples are only provided to more easily understand the present invention, and the contents of the present invention are not limited thereby.

[ Manufacturing example ]

Manufacturing example  1-1: Preparation of compound 1-1

10'-chlorospiro [fluorene-9,8'-indolo [3,2,1-de] acridine] (7.68 g, 22.99 mmol), dibiphenyl-4 in a 500 ml round bottom flask in a nitrogen atmosphere -After ylamine (5.61 g, 26.44 mmol) was completely dissolved in xylene (220 ml), sodium tert-butoxide (3.54 g, 36.79 mmol) was added, and Pd (t-Bu ₃ P) ₂ (0.24 g, 0.46 mmol) was added, followed by heating and stirring for 3 hours. After lowering the temperature to room temperature and filtering to remove the base, the xylene was concentrated under reduced pressure, and recrystallized twice with ethyl acetate (260 ml) to prepare compound 1-1 (12.34 g, yield: 77%).

MS: [M + H] ⁺ = 725

Manufacturing example  1-2: Preparation of compound 1-2

10'-chlorospiro [fluorene-9,8'-indolo [3,2,1-de] acridine] (8.12 g, 24.31 mmol), 4- (divi) in 500 ml round bottom flask in nitrogen atmosphere After phenyl-4-ylamino) phenylboronic acid (11.90 g, 26.74 mmol) was completely dissolved in THF (260 ml), a 2M aqueous potassium carbonate solution (130 ml) was added, and tetrakis- (triphenylphosphine) palladium ( 0.84 g, 0.73 mmol) was added, followed by heating and stirring for 3 hours. The temperature was reduced to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with THF (210 ml) to prepare compound 1-2 (14.46 g, yield: 74%).

MS: [M + H] ⁺ = 801

Manufacturing example  1-3: Preparation of compound 1-3

11'-chlorospiro [fluorene-9,8'-indolo [3,2] instead of 10'-chlorospiro [fluorene-9,8'-indolo [3,2,1-de] acridine] , 1-de] acridine] and using N- (biphenyl-4-yl) -9,9-dimethyl-9H-fluoren-2-amine instead of dibiphenyl-4-ylamine Compound 1-3 was manufactured by the same method as the method of preparing compound 1-1.

MS: [M + H] ⁺ = 765

Manufacturing example  1-4: Preparation of compound 1-4

11'-chlorospiro [fluorene-9,8'-indolo [3,2] instead of 10'-chlorospiro [fluorene-9,8'-indolo [3,2,1-de] acridine] , 1-de] acridine], except for using Compound 1-2, Compound 1-4 was prepared.

MS: [M + H] ⁺ = 801

Manufacturing example  1-5: Preparation of compound 1-5

Except using 4- (biphenyl-4-yl (9,9-dimethyl-9H-fluoren-2-yl) amino) phenylboronic acid instead of 4- (dibiphenyl-4-ylamino) phenylboronic acid Then, Compound 1-5 was produced by the same method as the production method of Compound 1-2.

MS: [M + H] ⁺ = 841

Manufacturing example  1-6: Preparation of compound 1-6

4- (biphenyl-4-yl (4- (dibenzo [b, d] furan-4-yl) phenyl) amino) phenylboronic acid is used instead of 4- (dibiphenyl-4-ylamino) phenylboronic acid Compound 1-6 was manufactured by the same method as the production method of Compound 1-2, except for the above.

MS: [M + H] ⁺ = 891

Manufacturing example  1-7: Preparation of compound 1-7

10'-chlorospiro [fluorene-9,8'-indolo [3,2] instead of 11'-chlorospiro [fluorene-9,8'-indolo [3,2,1-de] acridine] , 1-de] acridine] Compound 1-7 was manufactured by the same method as the production method of compound 1-5, except that the compound was used.

MS: [M + H] ⁺ = 841

Manufacturing example  1-8: Preparation of compound 1-8

10'-chlorospiro [fluorene-9,8'-indolo [3,2] instead of 11'-chlorospiro [fluorene-9,8'-indolo [3,2,1-de] acridine] Compound 1-8 was prepared by the same method as the method for preparing compound 1-6, except that, 1-de] acridine] was used.

MS: [M + H] ⁺ = 891

Manufacturing example  2-1: Preparation of compound 2-1

9-bromo-10- (naphthalen-1-yl) anthracene (8.12 g, 24.31 mmol), naphthalene-2-ylboronic acid (11.90 g, 26.74 mmol) in THF (260 ml) in a 500 ml round bottom flask in a nitrogen atmosphere. After completely dissolved in), 2M aqueous potassium carbonate solution (130 ml) was added, and tetrakis- (triphenylphosphine) palladium (0.84 g, 0.73 mmol) was added, followed by heating and stirring for 3 hours. The temperature was reduced to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with THF (210 ml) to prepare compound 2-1 (14.46 g, yield: 74%).

MS: [M + H] ⁺ = 431

Manufacturing example  2-2: Preparation of compound 2-5

Compound 2-5 was prepared by the same method as the method of preparing compound 2-1, except that phenanthrene-9-ylboronic acid was used instead of naphthalene-2-ylboronic acid.

MS: [M + H] ⁺ = 481

Manufacturing example  2-3: Preparation of compound 2-7

Compound 2-7 was prepared by the same method as the method of preparing compound 2-1, except that 10- (naphthalen-2-yl) anthracene-9-ylboronic acid was used instead of naphthalene-2-ylboronic acid.

MS: [M + H] ⁺ = 607

Manufacturing example  2-4: Preparation of compound 2-6

9-bromo-10- (naphthalen-1-yl) anthracene instead of 9-bromo-10- (naphthalen-2-yl) anthracene, except for using the same method as in the preparation of Compound 2-5 , Compound 2-6 was prepared.

MS: [M + H] ⁺ = 481

Manufacturing example  2-5: Preparation of compound 2-2

9-bromo-10-phenylanthracene (10.25 g, 30.87 mmol), 4- (naphthalen-2-yl) phenylboronic acid (8.42 g, 33.96 mmol) in THF (260 ml) in a 500 ml round bottom flask in a nitrogen atmosphere. After completely dissolved in), 2M aqueous potassium carbonate solution (130 ml) was added, tetrakis- (triphenylphosphine) palladium (1.07 g, 0.93 mmol) was added, followed by heating and stirring for 3 hours. The temperature was reduced to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with toluene (180 ml) to prepare compound 2-2 (10.55 g, yield: 75%).

MS: [M + H] ⁺ = 457

Manufacturing example  2-6: Preparation of compound 2-3

Compound 2-3 was prepared by the same method as the preparation method of Compound 2-2, except that 4- (naphthalen-1-yl) phenylboronic acid was used instead of 4- (naphthalen-2-yl) phenylboronic acid. It was prepared.

MS: [M + H] ⁺ = 481

Manufacturing example  2-7: Preparation of compound 2-4

Compound 2-4 was prepared by the same method as the method of preparing compound 2-2, except that 4-phenylnaphthalen-1-ylboronic acid was used instead of 4- (naphthalen-2-yl) phenylboronic acid.

MS: [M + H] ⁺ = 481

Manufacturing example  2-8: Preparation of compound 2-8

Compound 2-8 was prepared by the same method as the method of preparing compound 2-2, except that 10-phenylanthracene-9-ylboronic acid was used instead of 4- (naphthalen-2-yl) phenylboronic acid.

MS: [M + H] ⁺ = 507

Manufacturing example  3-1: Preparation of compound 3-1

1) Preparation of compound 3-A

1,4-dibromo-2,5-diiodobenzene (18.5 g, 0.038 mol) is (4-trifluoromethoxy) phenylboronic acid (16.0 g, 0.078 mol), tetrakis (triphenylphosphine) ) Palladium (0) (2.2 g), 2M potassium carbonate (114 ml), mixed with THF (360 ml), and refluxed and stirred for 8 hours under nitrogen. After cooling, it was extracted with water and dichloromethane, and further separated by a silica gel column (developing solvent: ethyl acetate / hexane = 10/1 (v / v)) to obtain a white solid (8.0 g, yield: 38.0%).

The white solid (8.5 g, 15.3 mmol), nickel powder (9.0 g, 76.6 mmol), potassium iodide (5.0 g, 30.4 mmol), iodine (0.19 g, 0.77 mmol) in dimethyl formaldehyde (20 ml) And mixed with reflux and stirred for 24 hours under argon. After completion of the reaction, 3% dilute hydrochloric acid (100 ml) and diethyl ether (40 ml) were added. Nickel solids were removed, extracted with water and diethyl ether, and separated by silica gel column (developing solvent: ethyl acetate / hexane = 10/1 (v / v)) to give compound 3-A as a white solid (5.4 g, Yield: 54.0%).

2) Preparation of compound 3-1

Malononitrile (1.7 g) was dissolved in 1,2-dimethoxyethane (60 ml) and cooled to −10 ° C. under nitrogen conditions. Sodium hydride (1.3 g) was added dropwise in 4 portions, stirred at room temperature for 20 minutes, and then re-cooled to 0 ° C. Compound 3-A (3.60 g, 5.54 mmol) prepared previously and tetrakis (triphenylphosphine) palladium (0.64 g, 0.55 mmol) were added and stirred at reflux for 8 hours. Then, it was separated with dilute hydrochloric acid and ethyl acetate, dried over anhydrous sodium sulfate, and filtered. After distilling ethyl acetate under reduced pressure, it was separated by a silica gel column (developing solvent: ethyl acetate) to obtain a solid (1.8 g, yield: 62.0%).

Next, after dissolving the solid (1.8 g) in acetonitrile (30 ml), dilute bromine water (20 ml) was added. After stirring for 20 minutes, an excess of distilled water was added to filter the precipitated solid, and washed with distilled water. Then, it was recrystallized from acetonitrile to obtain compound 3-1 (1.20 g).

MS: [M + H] ⁺ = 525

Manufacturing example  3-2: Preparation of compound 3-2

Compound 3-2 was prepared by the same method as the method for preparing compound 3-1, except that (4- (trifluoromethyl) phenylboronic acid was used instead of (4-trifluoromethoxy) phenylboronic acid. .

MS: [M + H] ⁺ = 493

Manufacturing example  3-3: Preparation of compound 3-3

1) Preparation of compound 3-B

Lithium 2,2,6,6-tetramethylpiperidide (100 mmol) was dissolved in THF (120 ml) and cooled to -78 ° C under nitrogen. 1,4-dibromo-2,5-difluorobenzene (27.2 g, 100 mmol) was dissolved in THF (60 ml), intubated at -78 ° C under nitrogen, and heated to room temperature. Thereafter, the reaction was terminated with an aqueous sodium thiosulfate solution, separated with ethyl acetate, dried over anhydrous sodium sulfate, and filtered. Separated by silica gel column (developing solvent: ethyl acetate / hexane = 10/1 (v / v)) to obtain a solid (26.3 g, yield: 66.0%).

Next, 2,2,6,6-tetramethylpiperidide lithium (100 mmol) was dissolved in THF (120 ml) and cooled to -78 ° C under nitrogen conditions. 1,4-dibromo-2,5-difluoro-3-iodobenzene (39.8 g, 100 mmol) was dissolved in THF (60 ml), intubated at -78 ° C under nitrogen, and at room temperature. It heated up. Then, the reaction was terminated with an aqueous sodium thiosulfate solution, separated with ethyl acetate, dried over anhydrous sodium sulfate, and filtered. Separated by silica gel column (developing solvent: ethyl acetate / hexane = 10/1) to obtain a solid (30.3 g, yield: 58.0%).

Next, 1,4-dibromo-2,5-difluoro-3,6-diiodobenzene (19.9 g, 0.038 mol) is replaced by (2-fluoro-4-trifluoromethoxy) phenylborone. Mix with acid (17.5 g, 0.078 mol), tetrakis (triphenylphosphine) palladium (0) (2.2 g), 2M potassium carbonate (114 ml), THF (360 ml) and reflux for 12 hours under nitrogen And stirred. After cooling, it was extracted with water and dichloromethane, and further separated by a silica gel column (developing solvent: ethyl acetate / hexane = 10/1 (v / v)) to obtain a white solid (7.8 g, yield: 34.7%). .

Next, the white solid (9.06 g, 15.3 mmol), nickel powder (9.0 g, 76.6 mmol), potassium iodide (5.0 g, 30.4 mmol), iodine (0.19 g, 0.77 mmol) were dimethylformaldehyde ( 20 ml), and refluxed and stirred for 24 hours under argon conditions. After completion of the reaction, 3% dilute hydrochloric acid (100 ml) and diethyl ether (40 ml) were added. The nickel solid was removed, extracted with water and diethyl ether, and separated by a silica gel column (developing solvent: ethyl acetate / hexane = 10/1 (v / v)) to give compound 3-B as a white solid (3.2 g, Yield: 30.4%).

2) Preparation of compound 3-3

Compound 3-3 (0.84 g) was prepared by the same method as the preparation of compound 3-1, except that compound 3-B (3.8 g) was used instead of compound 3-A (3.60 g).

MS: [M + H] ⁺ = 561

Manufacturing example  4-1: Preparation of compound 4-1

2- (9,9-diphenyl-9H-fluoren-4-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane in a 500 ml round bottom flask in a nitrogen atmosphere. (8.90 g, 20.04 mmol), 2- (biphenyl-4-yl) -4-chloro-6-phenyl-1,3,5-triazine (6.25 g, 18.22 mmol) in THF (240 ml) completely After dissolving, 2M potassium carbonate aqueous solution (120 ml) was added, tetrakis- (triphenylphosphine) palladium (0.63 g, 0.55 mmol) was added, followed by heating and stirring for 3 hours. The temperature was reduced to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with ethyl acetate (230 ml) to prepare compound 4-1 (8.85 g, yield: 78%).

MS: [M + H] ⁺ = 626

Manufacturing example  4-2: Preparation of compound 4-2

2- (biphenyl-4-yl) -4- (3-bromophenyl) -6 instead of 2- (biphenyl-4-yl) -4-chloro-6-phenyl-1,3,5-triazine -Compound 4-2 was prepared by the same method as the method of preparing compound 4-1, except that phenyl-1,3,5-triazine was used.

MS: [M + H] ⁺ = 702

Manufacturing example  4-3: Preparation of compound 4-3

2- (9,9-diphenyl-9H-fluoren-4-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane instead of 2- (9,9-di Same as the production method of compound 4-1, except that phenyl-9H-fluoren-2-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane is used. By the method, compound 4-3 was prepared.

MS: [M + H] ⁺ = 507

Manufacturing example  4-4: Preparation of compound 4-4

(4'-cyano- [1,1'-biphenyl] -4-yl) boronic acid (6.03 g, 27.04 mmol), 2- (4- (4-chloronaphthalene) in a 500 ml round bottom flask in a nitrogen atmosphere. -1-yl) phenyl) -4,6-diphenyl-1,3,5-triazine (11.53 g, 24.58 mmol) was completely dissolved in THF (220 ml) and 2M aqueous potassium carbonate solution (110 ml) was added. Then, tetrakis- (triphenylphosphine) palladium (0.85 g, 0.74 mmol) was added, followed by heating and stirring for 4 hours. The temperature was reduced to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with ethyl acetate (250 ml) to prepare compound 4-4 (12.22 g, yield: 81%).

MS: [M + H] ⁺ = 613

Manufacturing example  4-5: Preparation of compound 4-5

2- (4- (4-chloronaphthalen-2-yl) phenyl instead of 2- (4- (4-chloronaphthalen-1-yl) phenyl) -4,6-diphenyl-1,3,5-triazine ) -4,6-diphenyl-1,3,5-triazine was prepared in the same manner as in Compound 4-4, except that Triazine was used.

MS: [M + H] ⁺ = 613

[ Experimental Example  One]

compare Experimental Example  1-1

A glass substrate coated with a thin film coated with ITO (indium tin oxide) at a thickness of 1,000 에 was put in distilled water in which detergent was dissolved and washed with ultrasonic waves. At this time, Fischer Co. product was used as the detergent, and distilled water filtered secondarily by a filter of Millipore Co. was used as the distilled water. After washing the ITO for 30 minutes, ultrasonic cleaning was repeated twice with distilled water for 10 minutes. After washing with distilled water, ultrasonic cleaning was performed with a solvent of isopropyl alcohol, acetone, and methanol, followed by drying and then transported to a plasma cleaner. In addition, the substrate was washed for 5 minutes using oxygen plasma, and then transferred to a vacuum evaporator. On the prepared ITO transparent electrode, the following compound HAT (hexaazatriphenylene) was thermally vacuum-deposited to a thickness of 150 Pa to form a hole injection layer. On the hole injection layer, the following compound HT-1 (1150HT), which is a material for transporting holes, was vacuum deposited to form a hole transport layer. Subsequently, the following compound EB was vacuum-deposited to a thickness of 150 mm 2 on the hole transport layer to form an electron suppressing layer. Subsequently, the following compounds BH and BD with a thickness of 300 mm 3 were vacuum-deposited on the electron suppressing layer at a weight ratio of 25: 1 to form a light emitting layer. The following compound ET and the following compound LiQ (Lithium Quinolate) were vacuum deposited on the light emitting layer at a weight ratio of 1: 1 to form an electron injection and transport layer with a thickness of 360 mm 3. An organic light emitting device was manufactured by sequentially depositing lithium fluoride (LiF) to a thickness of 12 Å and aluminum to a thickness of 2,000 증착 on the electron injection and transport layer to form a cathode.

Was maintained at the deposition rate was 0.4 ~ 0.7Å / sec for organic material in the above process, the lithium fluoride of the cathode was 0.3Å / sec, aluminum is deposited at a rate of 2Å / sec, During the deposition, a vacuum 2 × 10 ^{- An} organic light emitting device was manufactured by maintaining ⁷ to 5 × 10 ⁻⁶ torr. In addition, the compound used is as follows.

compare Experimental Example  1-2 to 1-9

In Comparative Experimental Example 1-1, except that the compound prepared in the Preparation Example shown in Table 1 below, or the compound prepared in the Preparation Example shown in Table 1 below, in place of the EB compound, the An organic light emitting device was manufactured in the same manner as Comparative Experimental Example 1-1.

Experimental Example  1-1 to 1-16

In the Comparative Experimental Example 1-1, the organic light emitting device in the same manner as in Comparative Experimental Example 1-1, except that instead of the EB compound and the BH compound, the compound prepared in the Preparation Example shown in Table 1, respectively, was used. Was produced.

The manufacturing an organic light-emitting device at a current density of 20 mA / cm ² was measured drive voltage and luminous efficiency were measured for initial luminance compared to 95% of the time (T95) that is at a current density of 20 mA / cm ^2. The results are shown in Table 1 below.

Emissive
Host Electronic suppression layer Voltage
(V) Luminance
(cd / A) T95
(hr) Comparative Experimental Example 1-1 BH EB 4.33 5.93 270 Comparative Experimental Example 1-2 BH 1-1 4.24 6.12 280 Comparative Experimental Example 1-3 BH 1-3 4.15 6.16 280 Comparative Experimental Example 1-4 BH 1-6 4.17 6.04 285 Comparative Experimental Example 1-5 BH 1-8 4.23 6.17 290 Comparative Experimental Example 1-6 2-2 EB 4.22 6.05 285 Comparative Experimental Example 1-7 2-4 EB 4.23 6.18 280 Comparative Experimental Example 1-8 2-5 EB 4.13 6.09 275 Comparative Experimental Example 1-9 2-7 EB 4.16 6.21 280 Experimental Example 1-1 2-2 1-1 3.64 6.55 315 Experimental Example 1-2 2-4 1-1 3.63 6.53 310 Experimental Example 1-3 2-5 1-1 3.62 6.64 315 Experimental Example 1-4 2-7 1-1 3.68 6.75 300 Experimental Example 1-5 2-2 1-3 3.72 6.64 310 Experimental Example 1-6 2-4 1-3 3.73 6.66 305 Experimental Example 1-7 2-5 1-3 3.75 6.69 300 Experimental Example 1-8 2-7 1-3 3.74 6.67 315 Experimental Example 1-9 2-2 1-6 3.89 6.45 305 Experimental Example 1-10 2-4 1-6 3.86 6.41 300 Experimental Example 1-11 2-5 1-6 3.85 6.42 300 Experimental Example 1-12 2-7 1-6 3.82 6.44 305 Experimental Example 1-13 2-2 1-8 3.74 6.56 325 Experimental Example 1-14 2-4 1-8 3.72 6.54 320 Experimental Example 1-15 2-5 1-8 3.71 6.58 325 Experimental Example 1-16 2-7 1-8 3.79 6.55 325

As shown in Table 1, Comparative Experimental Examples 1-1 to 1-9 used compounds of Formula 1 instead of EB or compounds of Formula 2 instead of BH, and represented compounds represented by Formulas 1 and 2 The characteristics of the separately used device are shown. In addition, Experimental Examples 1-1 to 1-16 were used as the host of the electron suppressing layer and the light emitting layer, respectively, using the compound of Formula 1 and the compound of Formula 2, and the characteristics of the device to which the compounds represented by Formula 1 and Formula 2 were applied together. Indicates.

Accordingly, the organic light-emitting device of the experimental example according to the present invention compared to the comparative experimental example, the overall light-emitting efficiency is 7 to 10% higher, the driving voltage is lowered by about 10 to 12%, and the life is equal to or increased.

Through this, when the compound of Formula 1 of the present invention is used as an electron suppressing layer material and the compound of Formula 2 of the present invention is combined as a host material of the light emitting layer, the driving voltage, light emission efficiency, and life characteristics of the organic light emitting device are improved. You can see that you can.

[ Experimental Example  2]

compare Experimental Example  2-1 to 2-8

In Comparative Experimental Example 1-1, the organic light emitting device in the same manner as in Comparative Experimental Example 1-1, except that instead of the EB compound and the BH compound, the compound prepared in the Preparation Example shown in Table 2, respectively, was used. Was produced.

Experimental Example  2-1 to 2-4

In Comparative Experimental Example 1-1, the organic light emitting device in the same manner as in Comparative Experimental Example 1-1, except that instead of the EB compound and the BH compound, the compound prepared in the Preparation Example shown in Table 2, respectively, was used. Was produced.

Experimental Example  2-5 to 2-16

In Comparative Experimental Example 1-1, the HAT compound, the EB compound, and the BH compound, instead of using the compound prepared in the Preparation Example shown in Table 2, respectively, the same as in Comparative Experimental Example 1-1 An organic light emitting device was produced by the method.

The manufacturing an organic light-emitting device at a current density of 20 mA / cm ² was measured drive voltage and luminous efficiency were measured for initial luminance compared to 95% of the time (T95) that is at a current density of 20 mA / cm ^2. The results are shown in Table 2 below. For convenience of comparison, the results of Comparative Experimental Example 1-1 are also shown.

Hole injection layer Emissive
Host Electronic suppression layer Voltage
(V) Luminance
(cd / A) T95
(hr) Comparative Experimental Example 1-1 HAT BH EB 4.33 5.93 270 Comparative Experimental Example 2-1 HAT BH 1-2 4.24 6.12 280 Comparative Experimental Example 2-2 HAT BH 1-4 4.15 6.16 280 Comparative Experimental Example 2-3 HAT BH 1-5 4.17 6.04 285 Comparative Experimental Example 2-4 HAT BH 1-7 4.23 6.17 290 Comparative Experimental Example 2-5 HAT 2-1 EB 4.22 6.05 285 Comparative Experimental Example 2-6 HAT 2-3 EB 4.23 6.18 280 Comparative Experimental Example 2-7 HAT 2-6 EB 4.13 6.09 275 Comparative Experimental Example 2-8 HAT 2-8 EB 4.16 6.21 280 Experimental Example 2-1 HAT 2-1 1-2 3.64 6.55 315 Experimental Example 2-2 HAT 2-3 1-2 3.63 6.53 310 Experimental Example 2-3 HAT 2-6 1-2 3.62 6.54 315 Experimental Example 2-4 HAT 2-8 1-2 3.68 6.55 300 Experimental Example 2-5 3-1 2-1 1-4 3.72 6.54 310 Experimental Example 2-6 3-3 2-3 1-4 3.73 6.56 305 Experimental Example 2-7 3-1 2-6 1-4 3.75 6.59 300 Experimental Example 2-8 3-3 2-8 1-4 3.74 6.57 315 Experimental Example 2-9 3-3 2-1 1-5 3.59 6.69 305 Experimental Example 2-10 3-1 2-3 1-5 3.57 6.71 300 Experimental Example 2-11 3-3 2-6 1-5 3.59 6.68 300 Experimental Example 2-12 3-1 2-8 1-5 3.58 6.67 305 Experimental Example 2-13 3-3 2-1 1-7 3.74 6.56 325 Experimental Example 2-14 3-1 2-3 1-7 3.72 6.54 320 Experimental Example 2-15 3-1 2-6 1-7 3.71 6.58 325 Experimental Example 2-16 3-3 2-8 1-7 3.79 6.55 325

Similar to the results of Table 1, compared to the organic light emitting device of Comparative Experimental Example using a compound represented by Formula 1 and Formula 2 separately, the organic light emitting device of the Experimental Example applied with this has a luminous efficiency of 7 to 10% higher overall, driving The voltage was lowered by about 10 to 12%, and the lifespan was equivalent to increased.

Furthermore, when the compound of Formula 3 according to the present invention was used as the hole injection layer, the driving voltage tended to be lower. In particular, the organic light-emitting devices of Experimental Examples 2-9 to 2-12 showed relatively lower driving voltage and higher efficiency.

[ Experimental Example  3]

Experimental Example  3-1 to 3-13

In Comparative Experimental Example 1-1, the ET compound, the EB compound, and the BH compound, instead of using the compounds prepared in Preparation Examples shown in Table 3, respectively, the same as in Comparative Experimental Example 1-1 An organic light emitting device was manufactured by the method.

The manufacturing an organic light-emitting device at a current density of 20 mA / cm ² was measured drive voltage and luminous efficiency were measured for initial luminance compared to 95% of the time (T95) that is at a current density of 20 mA / cm ^2. The results are shown in Table 3 below. For convenience of comparison, the results of Comparative Experimental Examples 1-1 to 1-9 and Experimental Examples 1-1 to 1-3 are also shown.

Electron transport layer Emissive
Host Electronic suppression layer Voltage
(V) Luminance
(cd / A) T95
(hr) Comparative Experimental Example 1-1 ET BH EB 4.33 5.93 270 Comparative Experimental Example 1-2 ET BH 1-1 4.24 6.12 280 Comparative Experimental Example 1-3 ET BH 1-3 4.15 6.16 280 Comparative Experimental Example 1-4 ET BH 1-6 4.17 6.04 285 Comparative Experimental Example 1-5 ET BH 1-8 4.23 6.17 290 Comparative Experimental Example 1-6 ET 2-2 EB 4.22 6.05 285 Comparative Experimental Example 1-7 ET 2-4 EB 4.23 6.18 280 Comparative Experimental Example 1-8 ET 2-5 EB 4.13 6.09 275 Comparative Experimental Example 1-9 ET 2-7 EB 4.16 6.21 280 Experimental Example 1-1 ET 2-2 1-1 3.64 6.55 315 Experimental Example 1-2 ET 2-4 1-1 3.63 6.53 310 Experimental Example 1-3 ET 2-5 1-1 3.62 6.64 315 Experimental Example 3-1 4-1 2-7 1-1 3.68 6.75 345 Experimental Example 3-2 4-4 2-2 1-3 3.72 6.64 350 Experimental Example 3-3 4-1 2-4 1-3 3.73 6.66 345 Experimental Example 3-4 4-4 2-5 1-3 3.75 6.69 345 Experimental Example 3-5 4-4 2-7 1-3 3.74 6.67 350 Experimental Example 3-6 4-4 2-2 1-6 3.89 6.45 340 Experimental Example 3-7 4-1 2-4 1-6 3.86 6.41 345 Experimental Example 3-8 4-1 2-5 1-6 3.85 6.42 340 Experimental Example 3-9 4-1 2-7 1-8 3.82 6.44 340 Experimental Example 3-10 4-1 2-2 1-8 3.74 6.56 360 Experimental Example 3-11 4-4 2-4 1-8 3.72 6.54 365 Experimental Example 3-12 4-1 2-5 1-8 3.71 6.58 365 Experimental Example 3-13 4-4 2-7 1-7 3.79 6.55 360

As shown in Table 3, it can be seen that the life of the electron transport layer is further improved by combining the materials of Formula 4 together.

1: substrate 2: anode
3: hole transport layer 4: electron suppression layer
5: light emitting layer 6: electron transport layer
7: Cathode 8: Hole injection layer

Claims (13)

anode,
cathode,
A light emitting layer between the anode and the cathode, and
An electron suppressing layer between the anode and the light emitting layer,
The electron suppressing layer includes a compound represented by Formula 1 below,
The light emitting layer includes a compound represented by the formula (2),
Organic light emitting device:
[Formula 1]

In Chemical Formula 1,
Ar ₁ is biphenylyl, or dimethylfluorenyl,
Ar ₂ is terphenylyl, naphthyl, phenanthrenyl, triphenylenyl, dimethylfluorenyl, diphenylfluorenyl, spirobifluorenyl, dibenzofuranyl, or dibenzothiophenyl,
L ₁ , L ₂ , and L ₃ are each independently bonded; Substituted or unsubstituted C _6-60 arylene; Or C _2-60 heteroarylene containing one or more heteroatoms selected from the group consisting of substituted or unsubstituted O, N, Si and S,
[Formula 2]

In Chemical Formula 2,
Ar ₃ and Ar ₄ are each independently substituted or unsubstituted C _6-60 aryl; Or C _2-60 heteroarylene containing one or more heteroatoms selected from the group consisting of substituted or unsubstituted O, N, Si and S,
L ₄ and L ₅ are each independently bonded; Substituted or unsubstituted C _6-60 arylene; Or C _2-60 heteroarylene containing one or more heteroatoms selected from the group consisting of substituted or unsubstituted O, N, Si and S.
delete According to claim 1,
L ₁ , L ₂ , and L ₃ are each independently a bond, phenylene, biphenylylene, naphthylene, or dimethylfluorenylene,
Organic light emitting device.
According to claim 1,
The compound represented by Formula 1 is any one compound selected from the group consisting of,
Organic light emitting device:

According to claim 1,
Ar ₃ and Ar ₄ are each independently phenyl, biphenyline, terphenyline, naphthyl, phenanthrenyl, triphenylenyl, dimethylfluorenyl, or diphenylfluorenyl,
Organic light emitting device.
According to claim 1,
L ₄ and L ₅ are each independently a bond, phenylene, naphthylene, or anthracenyl,
Organic light emitting device.
According to claim 1,
The compound represented by Formula 2 is any one compound selected from the group consisting of,
Organic light emitting device:

According to claim 1,
A hole injection layer or a charge generating layer between the anode and the electron suppressing layer,
The hole injection layer or the charge generating layer comprises a compound represented by the formula (3),
Organic light emitting device:
[Formula 3]

In Chemical Formula 3,
R ₁ is any one selected from the group consisting of,

R ₂ is hydrogen, deuterium, halogen, cyano, or substituted or unsubstituted C _1-60 haloalkyl,
Ar ₅ is substituted or unsubstituted C _6-60 aryl; Or C _2-60 heteroarylene containing one or more heteroatoms selected from the group consisting of substituted or unsubstituted O, N, Si and S.
The method of claim 8,
Ar ₅ is phenyl, naphthyl, pyridine, quinazolinyl, or thiophenyl, wherein Ar ₅ is unsubstituted or from the group consisting of halogen, C _1-6 haloalkyl, C _1-6 haloalkoxy, and cyano Substituted with 1 to 5 substituents selected,
Organic light emitting device.
The method of claim 8,
The compound represented by Chemical Formula 3 is any one compound selected from the group consisting of:
Organic light emitting device:

According to claim 1,
Between the light emitting layer and the cathode includes an electron transport layer or a hole suppressing layer,
The electron transport layer or the hole inhibiting layer includes a compound represented by the following Chemical Formula 4, or a compound represented by the following Chemical Formula 5,
Organic light emitting device:
[Formula 4]

In Chemical Formula 4,
L ₆ and L ₇ are each independently a bond; Or substituted or unsubstituted C _6-60 arylene,
Ar ₆ and Ar ₇ are each independently substituted or unsubstituted C _6-60 aryl; Or C _2-60 heteroaryl containing one or more heteroatoms selected from the group consisting of substituted or unsubstituted O, N, Si and S,
[Formula 5]

In Chemical Formula 5,
X ₁ to X ₃ are each independently N, or CH,
L ₈ and L ₉ are each independently a bond; Or substituted or unsubstituted C _6-60 arylene,
Ar ₈ and Ar ₉ are each independently substituted or unsubstituted C _6-60 aryl; Or C _2-60 heteroaryl containing one or more heteroatoms selected from the group consisting of substituted or unsubstituted O, N, Si and S,
n is an integer from 1 to 5.
The method of claim 11,
The compound represented by the formula (4) is any one compound selected from the group consisting of,
Organic light emitting device:

The method of claim 11,
The compound represented by the formula (5) is any one compound selected from the group consisting of,
Organic light emitting device:

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