KR20200024726A - Organic light emitting device - Google Patents

Abstract

The present invention provides an organic light emitting device. The organic light emitting device comprises: an anode; a hole transport layer; a light emitting layer; a hole blocking layer; an electron transport layer; and a cathode. The organic light emitting device has a low driving voltage, high luminous efficiency, and excellent lifespan.

Description

Organic light emitting device

The present invention relates to an organic light emitting device having a low driving voltage, high luminous efficiency, and excellent lifespan.

In general, organic light emitting phenomenon refers to a phenomenon of converting 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, fast response time, excellent brightness, driving voltage and response speed characteristics, many studies have been conducted.

The organic light emitting device generally has a structure including an anode and a cathode and an organic layer between the anode and the cathode. The organic layer is often formed of a multi-layered structure composed of different materials to increase the efficiency and stability of the organic light emitting device, for example, it may be made of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer. When the voltage is applied between the two electrodes in the structure of the organic light emitting device, holes are injected into the organic material layer at the anode, and electrons are injected into the organic material layer, and excitons are formed when the injected holes and the electrons meet each other. When it falls back to the ground, it glows.

There is a continuous demand for the development of new materials for organic materials used in such organic light emitting devices.

Korean Patent Publication No. 10-2000-0051826

The present invention relates to an organic light emitting device having a low driving voltage, high luminous efficiency, and excellent lifespan.

In order to solve the said subject, this invention provides the following organic light emitting elements.

The organic light emitting device according to the present invention,

anode; Hole transport layer; Light emitting layer; Hole blocking layer; Electron transport layer; And a cathode,

The hole blocking layer includes a first compound having a dipole moment of 0 to 2,

The electron transport layer includes a second compound having a dipole moment of 3.5 to 10.

The organic light emitting device described above may have a low driving voltage, high luminous efficiency, and long lifespan by using a hole blocking layer and an electron transporting layer material satisfying a specific dipole moment value.

FIG. 1 shows an example of an organic light emitting device comprising a substrate 1, an anode 2, a hole transport layer 3, a light emitting layer 4, a hole blocking 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, a light emitting layer 4, a hole blocking layer 5, an electron transport layer 6, an electron injection layer 9. And an example of an organic light emitting element composed of a cathode 7.

Hereinafter, the present invention will be described in more detail to aid in understanding the present invention.

는 다른 치환기에 연결되는 결합을 의미한다.In this specification,

Means a bond connected to another substituent.

As used herein, the term "substituted or unsubstituted" is deuterium; Halogen group; Cyano group; Nitro group; Hydroxyl group; Carbonyl group; Ester group; Imide group; Amino group; Phosphine oxide groups; An alkoxy group; Aryloxy group; Alkyl thioxy group; Arylthioxy group; Alkyl sulfoxy groups; Aryl sulfoxy group; Silyl groups; Boron group; Alkyl groups; Cycloalkyl group; Alkenyl groups; Aryl group; Aralkyl group; Ar alkenyl group; Alkylaryl group; Alkylamine group; Aralkyl amine groups; Heteroarylamine group; Arylamine group; Aryl phosphine group; Or substituted or unsubstituted with one or more substituents selected from the group consisting of heteroaryl groups including one or more of N, O, and S atoms, or substituted or unsubstituted with two or more substituents in the above-described substituents. . For example, "a substituent to which two or more substituents are linked" may be a biphenyl group. That is, the biphenyl group may be an aryl group, and can be interpreted as a substituent to which two phenyl groups are linked.

Although carbon number of a carbonyl group in this specification is not specifically limited, It is preferable that it is C1-C40. Specifically, it may be a compound having a structure as follows, but is not limited thereto.

In the present specification, the ester group may be substituted with oxygen of the ester group having 1 to 25 carbon atoms, a straight chain, branched chain or cyclic alkyl group 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, although carbon number of an imide group is not specifically limited, It is preferable that it is C1-C25. Specifically, it may be a compound having a structure as follows, but is not limited thereto.

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

In the present specification, the boron group specifically includes, but is not limited to, trimethylboron group, triethylboron group, t-butyldimethylboron group, triphenylboron group, phenylboron group and the like.

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

In the present specification, the alkyl group may be linear or branched chain, carbon number is not particularly limited, but is preferably 1 to 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 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 -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 linear or branched chain, carbon number is not particularly limited, but is preferably 2 to 40. According to an exemplary embodiment, the alkenyl group has 2 to 20 carbon atoms. 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, stilbenyl 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 one 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 are not limited thereto.

In the present specification, the aryl group is not particularly limited, but preferably has 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to an exemplary embodiment, the aryl group has 6 to 30 carbon atoms. According to an exemplary embodiment, the aryl group has 6 to 20 carbon atoms. The aryl group may be a phenyl group, a biphenyl group, a terphenyl group, etc. as the monocyclic aryl group, but is not limited thereto. The polycyclic aryl group may be naphthyl group, anthracenyl group, phenanthrenyl group, pyrenyl group, peryllenyl 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, a fluorenyl group may be substituted, and two substituents may be bonded to each other to form a spiro structure. When the fluorenyl group is substituted,

And so on. However, the present invention is not limited thereto.

In the present specification, heteroaryl is a heteroaryl including one or more of O, N, Si, and S as a dissimilar element, and the number of carbon atoms is not particularly limited, but is preferably 2 to 60 carbon atoms. Examples of heteroaryl include thiophene group, furan group, pyrrole group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, pyrimidyl group, triazine group, acridil group, Pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidinyl group, pyrido pyrazinyl 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, isoxazolyl group, thiadiazolyl Groups, phenothiazinyl groups, dibenzofuranyl groups and the like, but are not limited thereto.

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

Meanwhile, in order to improve the efficiency of the organic light emitting device, a compound having a high dipole moment, that is, a high intramolecular polarity, is used as the electron transport layer material positioned in the electron transport region between the cathode and the light emitting layer. However, when the electron transport layer including the compound having a high dipole moment is in contact with the light emitting layer, the excitons generated at the interface may be lost, and thus the efficiency of the organic light emitting device may be lowered.

Accordingly, the organic light emitting device according to the present invention further comprises a hole blocking layer comprising a compound having a dipole moment value smaller than the compound included in the electron transport layer between the light emitting layer and the electron transport layer, the interface between the light emitting layer and the electron transport layer To prevent the excitons from being lost.

Specifically, the first compound included in the hole blocking layer has a dipole moment value of 0 to 2, the second compound included in the electron transport layer has a dipole moment value of 3.5 to 10. When the dipole moment value of the first compound is greater than 2, the first compound may not function as a hole blocking layer, and excitons are lost at the interface with the light emitting layer, thereby reducing the efficiency of the organic light emitting device. In addition, when the dipole moment value of the second compound is less than 3.5, exciton formation may be inhibited and the efficiency of the organic light emitting device may be reduced, and when it is more than 10, a large amount of exciton is formed and lost at the interface with the light emitting layer, thereby causing the organic light emitting device The lifetime of the can be lowered. Therefore, by using the first compound and the second compound having a dipole moment value in the above-described range in the hole blocking layer and the electron transport layer, respectively, it is possible to implement an organic light emitting device having high efficiency and a long life.

For example, the first compound may have a dipole moment value greater than 0 and less than 2, or 0.1 to 2, or 0.3 to 1.9, or 0.5 to 1.9. Also, for example, the second compound may have a dipole moment value of 3.5 to 9, or 4 to 8, or 4 to 7.

In addition, as the first compound included in the hole blocking layer and the second compound included in the electron transport layer have similar moieties, electrons may be smoothly moved to the cathode-electron transport layer-hole blocking layer-light emitting layer. . Therefore, it is necessary that the materials included in the hole blocking layer and the electron transport layer have a similar moiety and have a dipole moment in the above-described range. Including the first compound represented by the following formula (1) that does not contain a cyano group, and at the same time, the electron transport layer includes a second compound represented by the following formula (3) necessarily containing a cyano group.

As a result, the organic light-emitting device does not have a cyano group, and thus the hole blocking layer exhibiting a low dipole moment value prevents the loss of excitons in the light emitting layer and increases the density of the electron transport layer according to the compound substituted with the cyano group. Compared with an organic light emitting device having a hole blocking layer including a compound substituted with a compound and an electron transporting layer not containing a compound substituted with a cyano group, it exhibits high efficiency and increased lifetime.

On the other hand, the dipole moment in the present invention is a physical quantity indicating the degree of polarity, it can be calculated by the following equation (1), the unit uses "Debye (D)".

[Equation 1]

By calculating the molecular density (Molecular density) in the above formula (1), the value of the dipole moment can be obtained. For example, the molecular density can be obtained by calculating charges and dipoles for each atom using a method called Hirshfeld Charge Analysis, and calculating them according to the following equation. Obtain Dipole Moment.

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

Anode and cathode

As the anode material, a material having a large work function is generally preferred to facilitate hole injection into the organic material layer. 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), indium zinc oxide (IZO); Combinations of oxides with metals 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, 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; Multilayer structure materials such as LiF / Al or LiO ₂ / Al, and the like, but are not limited thereto.

In addition, a hole injection layer may be further included on the anode. The hole injection layer is made of a hole injection material, and has a capability of transporting holes as the hole injection material, has an effect of hole injection at the anode, excellent hole injection effect to the light emitting layer or the light emitting material, and The compound which prevents the movement to an electron injection layer or an electron injection material, and is excellent in thin film formation ability is preferable.

Preferably, the highest occupied molecular orbital (HOMO) of the hole injection material is between the work function of the positive electrode material and the HOMO of the surrounding organic layer. Specific examples of the hole injection material include metal porphyrin, oligothiophene, arylamine-based organic material, hexanitrile hexaazatriphenylene-based organic material, quinacridone-based organic material, and perylene Organic, anthraquinone, and polyaniline and polythiophene-based conductive polymers, but are not limited thereto.

Hole transport layer

The hole transport layer used in the present invention is a layer for receiving holes from the hole injection layer formed on the anode or the anode and transporting holes to the light emitting layer, and transporting holes from the anode or the hole injection layer with a hole transport material to the light emitting layer. Suitable materials are those with high mobility for holes.

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

Light emitting layer

The light emitting material included in the light emitting layer is a material capable of emitting light in the visible 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 with respect to fluorescence or phosphorescence is preferable.

Specific examples thereof include 8-hydroxyquinoline aluminum complex (Alq ₃ ); Carbazole series compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzo quinoline-metal compound; Benzoxazole, benzthiazole and benzimidazole series compounds; Poly (p-phenylenevinylene) (PPV) -based polymers; Spiro compounds; Polyfluorene, rubrene and the like, but are not limited thereto.

The light emitting layer may include a host material and a dopant material. The host material may be a condensed aromatic ring derivative or a hetero ring-containing compound. Specifically, the condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, and fluoranthene compounds, and the heterocyclic containing compounds include carbazole derivatives, dibenzofuran derivatives and ladder types. Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.

Dopant materials include aromatic amine derivatives, styrylamine compounds, boron complexes, fluoranthene compounds, metal complexes, and the like. Specifically, the aromatic amine derivatives include condensed aromatic ring derivatives having a substituted or unsubstituted arylamino group, and include pyrene, anthracene, chrysene and periplanthene having an arylamino group, and a styrylamine compound may be substituted or unsubstituted. At least one arylvinyl group is substituted with the above-described arylamine, and 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, styrylamine, styryldiamine, styryltriamine, styryltetraamine and the like, but is not limited thereto. In addition, the metal complex includes, but is not limited to, an iridium complex, a platinum complex, and the like.

Hole blocking layer

The hole blocking layer is formed on the light emitting layer, and specifically, the hole blocking layer is provided in contact with the light emitting layer to prevent excessive movement of holes, thereby increasing the hole-electron coupling probability to improve the efficiency of the organic light emitting device. It means a layer. In particular, in the present invention, the first compound having a dipole moment value of 0 to 2 is used as the material of the hole blocking layer, and in Formula 1, L ₁ to L ₃ , Ar ₁ , Ar _2, and A are not substituted with cyano. Do not.

The first compound is represented by the following Chemical Formula 1:

[Formula 1]

In Chemical Formula 1,

L ₁ to L ₃ are each independently a single bond; Or substituted or unsubstituted C _6-60 arylene,

Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted C _6-60 aryl; Or C _2-60 heteroaryl containing 1 to 3 heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S,

A is a monovalent substituent of the compound represented by the following formula (2),

[Formula 2]

In Chemical Formula 2,

T ₁ is a C _6-20 aromatic ring fused with a neighboring pentagram,

,

, 또는

이고,X ₁ is

,

, or

ego,

Y ₁ and Y ₂ are each, independently, hydrogen or deuterium, or together form a single bond, O, S, NR ₅ , CR ₆ R ₇ , or SiR ₈ R ₉ R ₁₀ ,

Z ₁ and Z ₂ are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted C _1-60 alkyl,

R ₁ to R ₁₀ are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted C _6-60 aryl; Or C _2-60 heteroaryl including one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S, or adjacent substituents are bonded to each other to form a C _6-60 spiro ring; C _6-60 aromatic ring; Or a C _2-60 heteroaromatic ring containing at least one N atom,

a1 to a4 are each independently an integer of 0 to 3,

when a1 to a4 are each 2 or more, the structures in the two or more parentheses are the same as or different from each other,

Provided that L ₁ to L ₃ , Ar ₁ , Ar _2, and A are not substituted with cyano.

At this time, in the formula 1 'L ₁ to L ₃ , Ar ₁ , Ar ₂ and A is not substituted with cyano' means, when L ₁ to L ₃ are each C _6-60 arylene, the substituents thereof, It means that all of the substituents of Ar _1, the substituents of Ar ₂ , and the substituents of R ₁ to R ₁₂ are not cyano groups.

In Formula 1, L ₁ to L ₃ may be each independently a single bond or C _6-20 arylene.

Specifically, L ₁ to L ₃ may each independently be a single bond, phenylene, biphenylylene, or naphthylene.

In addition, Ar ₁ and Ar ₂ are each independently C _6-20 aryl; Or C comprising one or two heteroatoms selected from the group consisting of N, O and S unsubstituted or substituted with one to three substituents selected from the group consisting of methyl, phenyl and pyridinyl _2-20 heteroaryl.

Specifically, Ar ₁ and Ar ₂ may each independently be phenyl, methylphenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, carbazolyl, dibenzofuranyl, dibenzothiophenyl, or pyridinyl. have.

In addition, R ₁ to R ₁₀ are each independently hydrogen; heavy hydrogen; C _6-60 aryl; Or C 2 _-60 heteroaryl comprising one or more heteroatoms selected from the group consisting of N, O and S; R ₅ combines with an adjacent substituent to form an indole or carbazole ring; Or R ₆ and R ₇ may combine with each other to form a fluorene and a spiro ring. In this case, forming the spiro structure means having a structure in which one carbon is connected to a contact point.

In addition, A may be represented by the following Chemical Formulas 2-1 to 2-9 according to the structure of X ₁ :

In Chemical Formulas 2-1 to 2-9,

Z ₁ and Z ₂ are each independently C _1-4 alkyl,

T ₁ is a benzene, naphthalene, or phenanthrene ring fused with a neighboring pentagram;

W ₁ is a single bond, O, S, or NR ₅ ,

Wherein R ₅ is C _6-20 aryl or may combine with an adjacent substituent to form an indole or carbazole ring,

R ₁ to R ₄ , R ₁₁ and R ₁₂ are each independently hydrogen or C _6-20 aryl,

a1 to a6 are each independently 0 or 1,

* Represents a position connected to L ₃ of the formula (1).

In Chemical Formula 2-1, Z ₁ and Z ₂ are methyl,

In Formula 2-4, W ₁ is a single bond, O, S, or NR ₇ , and when W ₁ is NR ₇ , R ₇ is phenyl, or is bonded to a neighboring substituent R ₃ to form an indole or carbazole ring. Forming and condensing with adjacent rings,

In Formulas 2-1 to 2-9, R ₁ to R ₄ , R ₁₁ and R ₁₂ may be hydrogen.

For example, A may be any one selected from the group consisting of Formulas 2a to 2k:

In Formulas 2a to 2k, W ₁ is a single bond, O, S, or NR ₅ , wherein the description of R ₅ is as defined in Formula 1, and * is a position connected to L ₃ of Formula 1 Indicates. Specifically, W ₁ may be a single bond, O, S, or N (phenyl).

Specifically, for example, A may be any one selected from the group consisting of:

In the above,

W 'is O or S,

* Represents a position connected to L ₃ of the formula (1).

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

On the other hand, the compound represented by the formula (1) can be prepared by the same production method as in Scheme 1 below.

Scheme 1

In Scheme 1, the description of L ₁ to L ₃ , Ar ₁ , Ar ₂ and A is as defined in Formula 1, X is halogen, preferably bromo or chloro. The reaction is a Suzuki coupling reaction, preferably performed in the presence of a palladium catalyst, and the reactor for the Suzuki coupling reaction can be modified as known in the art. The manufacturing method may be more specific in the manufacturing examples to be described later.

Electron transport layer

The electron transport layer refers to a layer formed between the hole blocking layer and the cathode to receive electrons from the electron injection layer to transport electrons to the light emitting layer. Specifically, the electron transport layer is provided in contact with the hole blocking layer. In particular, in the present invention, a second compound having a dipole moment value of 3.5 to 10 is used as a material of the electron transport layer, and in Formula 3, at least one of L ₄ to L ₆ , Ar ₃ , Ar _4, and B is cyano. Is substituted.

The second compound is represented by Formula 3:

[Formula 3]

In Chemical Formula 3,

L ₄ to L ₆ are each independently a single bond; Or substituted or unsubstituted C _6-60 arylene,

Ar ₃ and Ar ₄ are each independently a substituted or unsubstituted C _6-60 aryl; Or C _2-60 heteroaryl containing 1 to 3 heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S,

B is a monovalent substituent of the compound represented by the following formula (4),

[Formula 4]

In Chemical Formula 4,

T ₂ is a C _6-20 aromatic ring fused with a neighboring pentagram,

, 또는

이고,X ₂ is

, or

ego,

Y ₃ and Y ₄ are each independently hydrogen, deuterium, or cyano, or together form a single bond, O, S, NQ ₅ , CQ ₆ Q ₇ , or SiQ ₈ Q ₉ Q ₁₀ ,

Q ₁ to Q ₁₀ are each independently hydrogen; heavy hydrogen; Cyano; Substituted or unsubstituted C _6-60 aryl; Or C _2-60 heteroaryl including one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S, or adjacent substituents are bonded to each other to form a C _6-60 spiro ring; C _6-60 aromatic ring; Or a C _2-60 heteroaromatic ring containing at least one N atom,

b1 to b4 are each independently an integer of 0 to 3,

when b1 to b4 are each 2 or more, the structures in the two or more parentheses are the same as or different from each other,

Provided that at least one of L ₄ to L ₆ , Ar ₃ , Ar _4, and B is substituted with cyano.

In this case, the meaning of 'at least one of L ₄ to L ₆ , Ar ₃ , Ar ₄ and B is substituted with cyano' in Formula 3 means that L ₄ to L ₆ are each C _6-60 arylene. At least one of a substituent, a substituent of Ar ₃ , a substituent of Ar ₄ , and a substituent of Q (Q ₁ to Q ₁₂ ) is a cyano group.

Specifically, in the case where L ₄ to L ₆ of Formula 3 are each C _6-60 arylene, one to _three of the substituents Ar _3, the substituents of Ar ₄ , and the substituents of B (Q ₁ to Q ₁₂ ) The dog may be a cyano group.

Preferably, one of L ₄ to L ₆ , Ar ₃ , Ar ₄ and B is substituted with cyano. In other words, when L ₄ to L ₆ of Formula 3 are each C _6-60 arylene, one of a substituent of Ar ₃ , a substituent of Ar ₄ , and a substituent of B (Q ₁ to Q ₁₂ ), or Two may be cyano groups.

In addition, the term "substituted with cyano" in the definition of the substituent herein means that one or more hydrogen, preferably one or two hydrogen of the hydrogen contained in the substituent is substituted with a cyano group.

The second compound is represented by the formula 3A, 3B, 3C, 3D, 3E, or 3F,

Organic light emitting device:

[Formula 3A]

In Chemical Formula 3A,

L ₄ to L ₆ are each independently a single bond; Or C _6-20 arylene unsubstituted or substituted with cyano,

Ar ₃ and Ar ₄ are each independently C _6-20 aryl unsubstituted or substituted with methyl or cyano,

Q ₁ to Q ₃ are each independently hydrogen; heavy hydrogen; Or cyano,

Provided that at least one of L ₄ to L ₆ is C _6-20 arylene substituted with cyano;

At least one of Ar ₃ and Ar ₄ is C _6-20 aryl substituted with cyano; or

At least one of Q ₁ to Q ₃ is cyano,

[Formula 3B]

[Formula 3C]

In Chemical Formulas 3B and 3C,

W ₂ is O, S, NQ ₅ , CQ ₆ Q ₇ , or SiQ ₈ Q ₉ Q ₁₀ ,

L ₄ to L ₆ are each independently a single bond; Or C _6-20 arylene unsubstituted or substituted with cyano,

Ar ₃ and Ar ₄ are each independently C _6-20 aryl unsubstituted or substituted with methyl or cyano,

Q ₁ to Q ₁₀ are each independently hydrogen; heavy hydrogen; Cyano; Or C _6-60 aryl unsubstituted or substituted with cyano,

Provided that at least one of L ₄ to L ₆ is C _6-20 arylene substituted with cyano;

At least one of Ar ₃ and Ar ₄ is C _6-20 aryl substituted with cyano; or

At least one of Q ₁ to Q ₁₀ is cyano or C _6-60 aryl substituted with cyano,

[Formula 3D]

[Formula 3E]

In Chemical Formulas 3D and 3E,

T ₂ is a benzene, naphthalene, or phenanthrene ring fused with a neighboring pentagram;

L ₄ to L ₆ are each independently a single bond; Or C _6-20 arylene unsubstituted or substituted with cyano,

Ar ₃ and Ar ₄ are each independently C _6-20 aryl unsubstituted or substituted with methyl or cyano,

Q ₁ to Q ₄ are each independently hydrogen; heavy hydrogen; Or cyano,

Provided that at least one of L ₄ to L ₆ is C _6-20 arylene substituted with cyano;

At least one of Ar ₃ and Ar ₄ is C _6-20 aryl substituted with cyano; or

At least one of Q ₁ to Q ₄ is cyano,

[Formula 3F]

In Chemical Formula 3F,

L ₄ to L ₆ are each independently a single bond; Or C _6-20 arylene unsubstituted or substituted with cyano,

Ar ₃ and Ar ₄ are each independently C _6-20 aryl unsubstituted or substituted with methyl or cyano,

Q ₁ to Q ₄ , Q ₁₁ and Q ₁₂ are each independently hydrogen; heavy hydrogen; Or cyano,

Provided that at least one of L ₄ to L ₆ is C _6-20 arylene substituted with cyano;

At least one of Ar ₃ and Ar ₄ is C _6-20 aryl substituted with cyano; or

At least one of Q ₁ to Q ₄ , Q ₁₁ and Q ₁₂ is cyano.

In addition, in the present specification, the term "C _6-20 aryl unsubstituted or substituted with methyl or cyano" in the definition of a substituent means unsubstituted C _6-20 aryl; C _6-20 aryl substituted with one or more methyl; C _6-20 aryl substituted with one or more cyano; Or C _6-20 aryl substituted with one or more cyano and one or more methyl.

In addition, L ₄ to L ₆ are each independently a single bond; Substituted or unsubstituted phenylene; Substituted or unsubstituted biphenylylene; Substituted or unsubstituted terphenylylene; Or substituted or unsubstituted naphthylene.

For example, L ₄ to L ₆ are each independently a single bond; Phenylene unsubstituted or substituted with cyano; Biphenylylene, unsubstituted or substituted with cyano; Terphenylylene, unsubstituted or substituted with cyano; Or naphthylene unsubstituted or substituted with cyano.

In addition, Ar ₃ and Ar ₄ may each independently be C _6-20 aryl unsubstituted or substituted with methyl or cyano.

For example, Ar ₃ and Ar ₄ are each independently phenyl unsubstituted or substituted with cyano; Biphenylyl unsubstituted or substituted with cyano; Or terphenylyl unsubstituted or substituted with cyano; Or 9,9-dimethylfluorene unsubstituted or substituted with cyano.

Specifically, for example, Ar ₁ and Ar ₂ are each independently phenyl unsubstituted or substituted with one or two cyano; Biphenylyl unsubstituted or substituted with one or two cyano; Or terphenylyl unsubstituted or substituted with one or two cyano; Or 9,9-dimethylfluorene unsubstituted or substituted with one or two cyanos.

In addition, in Formula 4, Q ₁ to Q ₁₀ corresponding to the substituent of B are each independently hydrogen; heavy hydrogen; Cyano; C _6-20 aryl unsubstituted or substituted with cyano; Or C _2-60 heteroaryl containing 1 to 3 heteroatoms selected from the group consisting of N, O and S unsubstituted or substituted with cyano, or Q ₅ is combined with an adjacent substituent to form an indole or To form a carbazole ring; Or Q ₆ and Q ₇ may combine with each other to form a fluorene and a spiro ring.

In addition, Q ₁ to Q ₄ , Q ₁₁ and Q ₁₂ may be each independently hydrogen or cyano. In addition, Q ₅ to Q ₁₀ are each independently hydrogen; heavy hydrogen; Cyano; C _6-20 aryl unsubstituted or substituted with cyano; Or C _2-60 heteroaryl containing 1 to 3 heteroatoms selected from the group consisting of N, O and S unsubstituted or substituted with cyano.

In addition, B may be represented by the following Chemical Formulas 4-1 to 4-8 according to the structure of X ₂ :

In Chemical Formulas 4-1 to 4-8,

T ₂ is a benzene, naphthalene, or phenanthrene ring fused with a neighboring pentagram;

W ₂ is a single bond, O, S, or NQ ₅ ,

Q ₅ is C _6-20 aryl or may combine with an adjacent substituent to form an indole or carbazole ring,

Q ₁ to Q ₄ , Q ₁₁ and Q ₁₂ are each independently hydrogen, cyano, or C _6-20 aryl,

b1 to b6 are each independently 0 or 1,

* 'Represents a position connected to L ₆ of the formula (3).

Specifically, in Chemical Formulas 4-1 to 4-8,

W ₂ is O, S, or N (C _6-20 aryl),

Q ₁ to Q ₄ , Q ₁₁ and Q ₁₂ may be each independently hydrogen or cyano.

For example, B may be any one selected from the group consisting of Formulas 4a to 4h:

In Chemical Formulas 4a to 4h,

W ₂ is O, S, or N (phenyl), and Q ₁ to Q ₆ may each independently be hydrogen or cyano.

In this case, in Chemical Formula 4a, Q ₁ to Q ₃ are all hydrogen; Or one of Q ₁ to Q ₃ is cyano, the other is hydrogen,

In Formulas 4b to 4f and 4h, Q ₁ to Q ₄ are all hydrogen; Or one of Q ₁ to Q ₄ is cyano, the other is hydrogen,

In Formula 4g, Q ₁ to Q ₄ , Q ₁₁ and Q ₁₂ are all hydrogen; Or one of Q ₁ to Q ₄ , Q ₁₁ and Q ₁₂ may be cyano, and the other may be hydrogen.

Specifically, for example, B may be any one selected from the group consisting of:

In the above, Q ₁ to Q ₄ , Q ₁₁ and Q ₁₂ are each independently hydrogen or cyano, and * ′ represents a position connected to L ₆ of Chemical Formula 3 above.

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

On the other hand, the compound represented by the formula (3) can be prepared by a manufacturing method such as Scheme 2, for example.

Scheme 2

In Scheme 2, the description of L ₄ to L ₆ , Ar ₃ , Ar ₄ and B is the same as defined in Formula 3, X is halogen, preferably bromo or chloro. The reaction is a Suzuki coupling reaction, preferably performed in the presence of a palladium catalyst, and the reactor for the Suzuki coupling reaction can be modified as known in the art. The manufacturing method may be more specific in the manufacturing examples to be described later.

Electron injection layer

The electron injection layer is a layer that injects electrons from an electrode, and has a capability of transporting electrons, an electron injection effect from a cathode, an excellent electron injection effect on a light emitting layer or a light emitting material, and a compound having excellent thin film formation ability. desirable. In addition, the electron injection layer may also serve as the above-described electron transport layer.

Specific examples of the electron injection material may include LiF, NaCl, CsF, Li ₂ O, BaO, fluorenone, anthraquinomimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, Perylenetetracarboxylic acid, preorenylidene methane, anthrone and the like, derivatives thereof, metal complex compounds and nitrogen-containing 5-membered ring derivatives, and the like, but are not limited thereto.

Organic light emitting device

The structure of the organic light emitting device according to the present invention is illustrated in FIG. 1. FIG. 1 shows an example of an organic light emitting device comprising a substrate 1, an anode 2, a hole transport layer 3, a light emitting layer 4, a hole blocking layer 5, an electron transport layer 6, and a cathode 7. It is shown. In such a structure, the compound represented by Formula 1 may be included in the hole blocking layer, and the compound represented by Formula 3 may be included in the electron transport layer. In this case, the electron transport layer and the electron injection layer may be provided as one layer such as an electron injection and transport layer.

2 shows a substrate 1, an anode 2, a hole injection layer 8, a hole transport layer 3, a light emitting layer 4, a hole blocking layer 5, an electron transport layer 6, an electron injection layer 9. And an example of an organic light emitting element composed of a cathode 7. The compound represented by Formula 1 may be included in the hole blocking layer, and the compound represented by Formula 3 may be included in the electron transport layer. In this case, the electron transport layer and the electron injection layer may be provided as one layer such as an electron injection and transport layer.

The organic light emitting device according to the present invention can be manufactured by sequentially stacking the above-described configuration. At this time, by using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation, a metal or conductive metal oxide or an alloy thereof is deposited on the substrate to form an anode. After forming the above-described respective layers, it can be prepared by depositing a material that can be used as a cathode thereon. In addition to the above method, an organic light emitting device may be manufactured by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate. In addition, the light emitting layer may be formed of a host and a dopant not only by vacuum deposition but also by solution coating. Here, the solution coating method means spin coating, dip coating, doctor blading, inkjet printing, screen printing, spray method, roll coating, etc., but is not limited thereto.

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

Meanwhile, the organic light emitting device according to the present invention may be a top emission type, a bottom emission type, or a double side emission type according to a material used.

Fabrication of the organic light emitting device will be described in detail in the following Examples. However, the following examples are only for illustrating the present invention, and the scope of the present invention is not limited thereto.

Preparation of Second Compound

Production Example  3-1: Preparation of Compound 3-1

Compound A1 (10 g, 25.2 mmol) and Compound B1 (11.6 g, 25.2 mmol) were added to tetrahydrofuran (150 mL). 2M K ₂ CO ₃ (100 mL), tris (dibenzylideneacetone) dipalladium (0) (Pd (dba) ₂ , 0.6 g), and tetracyclohexylphosphine (PCy _3, 0.6 g) were added thereto. It was stirred and refluxed for 5 hours. After cooling to room temperature, the solid produced by filtration was recrystallized with chloroform and ethanol to prepare the compound 3-1 (13.4 g, yield 82%).

MS: [M + H] ⁺ = 651

Production Example  2: Preparation of Compound 3-2

Compound A2 (10 g, 21.2 mmol) and Compound B2 (9.2 g, 21.2 mmol) were added to tetrahydrofuran (150 mL). 2M K ₂ CO ₃ (100 mL), Pd (dba) ₂ (0.5 g), and PCy ₃ (0.5 g) were added, followed by stirring and reflux for 5 hours. After cooling to room temperature, the solid produced by filtration was recrystallized with chloroform and ethanol to prepare the compound 3-2 (10.5 g, yield 71%).

MS: [M + H] ⁺ = 701

Production Example  3: Preparation of Compound 3-3

Compound A3 (10 g, 24.3 mmol) and Compound B3 (11.2 g, 24.3 mmol) were added to tetrahydrofuran (150 mL). 2M K ₂ CO ₃ (100 mL), Pd (dba) ₂ (0.6 g), and PCy ₃ (0.6 g) were added, followed by stirring and reflux for 5 hours. After cooling to room temperature, the solid produced by filtration was recrystallized with chloroform and ethanol to prepare the compound 3-3 (12.6 g, yield 78%).

MS: [M + H] ⁺ = 665

Production Example  4: Preparation of Compound 3-4

Compound A4 (10 g, 22.9 mmol) and Compound B2 (10 g, 22.9 mmol) were added to tetrahydrofuran (150 mL). 2M K ₂ CO ₃ (100 mL), Pd (dba) ₂ (0.6 g), and PCy ₃ (0.6 g) were added, followed by stirring and reflux for 5 hours. After cooling to room temperature, the solid produced by filtration was recrystallized with chloroform and ethanol to prepare the compound 3-4 (10.4 g, yield 68%).

MS: [M + H] ⁺ = 665

Production Example  5: Preparation of Compound 3-5

Compound A5 (10 g, 17.9 mmol) and Compound B4 (9.6 g, 17.9 mmol) were added to tetrahydrofuran (150 mL). 2M K ₂ CO ₃ (100 mL), Pd (dba) ₂ (0.5 g), and PCy ₃ (0.5 g) were added, followed by stirring and reflux for 5 hours. After cooling to room temperature, the solid produced by filtration was recrystallized with chloroform and ethanol to prepare the compound 3-5 (9.9 g, yield 62%).

MS: [M + H] ⁺ = 890

Production Example  6: Preparation of Compound 3-6

Compound A3 (10 g, 24.3 mmol) and Compound B5 (11.2 g, 24.3 mmol) were added to tetrahydrofuran (150 mL). 2M K ₂ CO ₃ (100 mL), Pd (dba) ₂ (0.6 g), and PCy ₃ (0.6 g) were added, followed by stirring and reflux for 5 hours. After cooling to room temperature, the solid produced by filtration was recrystallized with chloroform and ethanol to prepare the compound 3-6 (12.9 g, yield 80%).

MS: [M + H] ⁺ = 665

Production Example  7: Preparation of Compound 3-7

Compound 3-7 was prepared in the same manner as in Preparation Example 3-1 except that Compound A6 was used instead of Compound A1 and Compound B6 was used instead of Compound B1 in Preparation Example 3-1.

MS: [M + H] ⁺ = 650

Production Example  8: Preparation of Compound 3-8

Compound 3-8 was prepared in the same manner as in Preparation Example 3-1 except that Compound A4 was used instead of Compound A1 and Compound B7 was used instead of Compound B1 in Preparation Example 3-1.

MS: [M + H] ⁺ = 741

Production Example  9: Preparation of Compound 3-9

Compound 3-9 was prepared by the same method as Preparation Example 3-1, except that Compound A7 was used instead of Compound A1 and Compound B5 was used instead of Compound B1 in Preparation Example 3-1.

MS: [M + H] ⁺ = 651

Production Example  3-10: Preparation of Compound 3-10

Compound 3-10 was prepared in the same manner as in Preparation Example 3-1 except that Compound A3 was used instead of Compound A1 and Compound B6 was used instead of Compound B1 in Preparation Example 3-1.

MS: [M + H] ⁺ = 665

Production Example  3-11: Preparation of Compound 3-11

Compound 3-11 was prepared in the same manner as in Preparation Example 3-1 except that Compound A3 was used instead of Compound A1 and Compound B7 was used instead of Compound B1 in Preparation Example 3-1.

MS: [M + H] ⁺ = 665

Production Example  3-12: Preparation of Compound 3-12

Compound 3-12 was prepared in the same manner as in Preparation Example 3-1, except that Compound A4 was used instead of Compound A1 and Compound B7 was used instead of Compound B1 in Preparation Example 3-1.

MS: [M + H] ⁺ = 741

Preparation of First Compound

Production Example  1-1: Preparation of Compound 1-1

Compound 1-1 was prepared in the same manner as in Preparation Example 3-1 except that Compound A3 was used instead of Compound A1 and Compound C1 was used instead of Compound B1 in Preparation Example 3-1.

MS: [M + H] ⁺ = 729

Production Example  1-2: Preparation of Compound 1-2

Compound 1-2 was prepared in the same manner as in Preparation Example 3-1, except that Compound A3 was used instead of Compound A1 and Compound C2 was used instead of Compound B1 in Preparation Example 3-1.

MS: [M + H] ⁺ = 654

Production Example  1-3: Preparation of Compound 1-3

Compound 1-3 was prepared in the same manner as in Preparation Example 3-1, except that Compound A3 was used instead of Compound A1 and Compound C3 was used instead of Compound B1 in Preparation Example 3-1.

MS: [M + H] ⁺ = 640

Production Example  1-4: Preparation of Compound 1-4

Compound 1-4 was prepared in the same manner as in Preparation Example 3-1 except that Compound A8 was used instead of Compound A1 and Compound C4 was used instead of Compound B1.

MS: [M + H] ⁺ = 592

Production Example  1-5: Preparation of Compound 1-5

Compound 1-5 was prepared in the same manner as in Preparation Example 3-1 except that Compound A3 was used instead of Compound A1 and Compound C5 was used instead of Compound B1 in Preparation Example 3-1.

MS: [M + H] ⁺ = 726

Production Example  1-6: Preparation of Compound 1-6

Compound 1 was prepared in the same manner as in Preparation Example 3-1, except that Compound A8 was used instead of Compound A1 in Preparation Example 3-1, and Compound C6 was used instead of Compound B1 in Preparation Example 3-1. -6 was prepared.

MS: [M + H] ⁺ = 690

Production Example  1-7: Preparation of Compound 1-7

Compound 1-7 was prepared in the same manner as in Preparation Example 3-1 except that Compound A3 was used instead of Compound A1 and Compound C7 was used instead of Compound B1 in Preparation Example 3-1.

MS: [M + H] ⁺ = 716

Production Example  1-8: Preparation of Compound 1-8

Compound 1-8 was prepared in the same manner as in Preparation Example 3-1 except that Compound A9 was used instead of Compound A1 and Compound C8 was used instead of Compound B1 in Preparation Example 3-1.

MS: [M + H] ⁺ = 713

Production Example  1-9: Preparation of Compound 1-9

Compound 1-9 was prepared by the same method as Preparation Example 3-1, except that Compound A10 was used instead of Compound A1 and Compound B9 was used instead of Compound B1 in Preparation Example 3-1.

MS: [M + H] ⁺ = 536

Production Example  1-10: Preparation of Compound 1-10

Compound 1-10 was prepared in the same manner as in Preparation Example 3-1, except that Compound A11 was used instead of Compound A1 and Compound C10 was used instead of Compound B1 in Preparation Example 3-1.

MS: [M + H] ⁺ = 650

Production Example  1-11: Preparation of Compound 1-11

Compound 1-11 was prepared in the same manner as in Preparation Example 3-1 except that Compound A12 was used instead of Compound A1 and Compound C11 was used instead of Compound B1 in Preparation Example 3-1.

MS: [M + H] ⁺ = 639

Production Example  1-12: Preparation of Compound 1-12

Compound 1-12 was prepared in the same manner as in Preparation Example 3-1, except that Compound A9 was used instead of Compound A1 and Compound C12 was used instead of Compound B1 in Preparation Example 3-1.

MS: [M + H] ⁺ = 713

Production Example  1-13: Preparation of Compound 1-13

Compound 1-13 was prepared by the same method as Preparation Example 3-1, except that Compound 13 was used instead of Compound A1 and Compound C13 was used instead of Compound B1 in Preparation Example 3-1.

MS: [M + H] ⁺ = 578

Example  One

A glass substrate (corning 7059 glass) coated with ITO (Indium Tin Oxide) having a thickness of 1000 Å was placed in distilled water in which a dispersant was dissolved, and ultrasonically washed. Fischer Co. was used for the detergent, and Millipore Co. Secondary filtered distilled water was used as a filter of the product. After ITO was washed for 30 minutes, ultrasonic washing was repeated 10 times with distilled water twice. After washing the distilled water, the ultrasonic washing in the order of isopropyl alcohol, acetone, methanol solvent and dried.

Hexanitrile hexaazatriphenylene (HATCN) was thermally vacuum deposited to a thickness of 500 kPa on the prepared ITO transparent electrode to form a hole injection layer. A hole transport layer was formed by vacuum depositing HT1 (400 kPa), a material for transporting holes, thereon.

On the hole transport layer, the host H1 and the dopant D1 compound were vacuum deposited to a thickness of 300 kPa to form a light emitting layer.

Compound 1-1 prepared in Preparation Example 1-1 was deposited to a thickness of 50 kHz on the emission layer to form a hole blocking layer. Compound 3-1 prepared in Preparation Example 3-1 and LiQ (Lithium Quinolate) were vacuum-deposited on the hole blocking layer in a weight ratio of 1: 1 to form an electron transport layer having a thickness of 350 Pa.

The organic light emitting device was manufactured by sequentially depositing lithium fluoride (LiF) and aluminum having a thickness of 2,000 Å on the electron transport layer to form a electron injection layer and a cathode.

In the above process, the deposition rate of the organic material was maintained at 0.4 ~ 0.7 Å / sec, the lithium fluoride of the cathode was maintained at the deposition rate of 0.3 Å / sec, aluminum is 2 Å / sec, the vacuum degree during deposition is 2 ⅹ 10 ^-7 An organic light emitting device was manufactured by maintaining ˜5 × 10 ⁻⁶ torr.

The compound used in Example 1 is as follows.

Example  2 to Example  12, Reference Example  1 and Comparative example  1 to 3

Except for using the compounds shown in Table 2 below instead of compound 1-1 as the hole blocking layer material in Example 1, and using the compounds shown in Table 2 below instead of compound 3-1 as the electron transport layer, An organic light emitting device was manufactured in the same manner as in Example 1.

The hole blocking layer material compounds 1-1 to 1-13 used in the above examples are summarized as follows.

Examples of the electron transport layer material compound 3-1 to 3-12 used in the above embodiment are as follows.

The hole blocking layer material HB1 and the hole transport layer material ET1, ET2 and ET3 used in the reference example and the comparative example are summarized as follows.

In this case, the dipole moments of the compounds used in Examples and Comparative Examples are shown in Table 1 below.

Hole blocking layer Electron transport layer compound Dipole moment
(Debye) compound Dipole moment
(Debye) Compound 1-1 1.49 Compound 3-1 5.62 Compound 1-2 1.27 Compound 3-2 5.81 Compound 1-3 0.62 Compound 3-3 5.29 Compound 1-4 1.11 Compound 3-4 4.67 Compound 1-5 0.65 Compound 3-5 5.17 Compound 1-6 1.35 Compound 3-6 6.87 Compound 1-7 1.08 Compound 3-7 5.10 Compound 1-8 0.80 Compound 3-8 5.21 Compound 1-9 0.64 Compound 3-9 5.11 Compound 1-10 0.97 Compound 3-10 5.79 Compound 1-11 1.83 Compound 3-11 5.23 Compound 1-12 1.38 Compound 3-12 4.71 Compound 1-13 0.86 ET1 5.55 HB1 6.00 ET2 0.78 ET3 0.80

Experimental Example

For the organic light emitting diodes manufactured in Examples and Comparative Examples, the driving voltage and luminous efficiency at a current density of 10 mA / cm ² , and the time of becoming 98% of the initial luminance at a current density of 20 mA / cm ² (LT98 ) Was measured, and the results are shown in Table 2 below.

Hole blocking layer
compound Electron transport layer
compound Driving voltage
(V
@ 10mA / cm ² ) Current efficiency
(cd / A
@ 10mA / cm ² ) LT98
(hr
@ 20mA / cm ² ) Example 1 Compound 1-1 Compound 3-1 3.80 5.33 51 Example 2 Compound 1-5 Compound 3-2 3.81 5.34 60 Example 3 Compound 1-7 Compound 3-3 3.90 5.29 62 Example 4 Compound 1-13 Compound 3-4 3.88 5.30 60 Example 5 Compound 1-2 Compound 3-5 3.85 5.25 55 Example 6 Compound 1-10 Compound 3-6 3.90 5.31 53 Example 7 Compound 1-3 Compound 3-7 3.65 5.49 42 Example 8 Compound 1-6 Compound 3-8 3.91 5.21 49 Example 9 Compound 1-8 Compound 3-9 3.90 5.22 51 Example 10 Compound 1-9 Compound 3-10 3.99 5.21 60 Example 11 Compound 1-11 Compound 3-11 4.01 5.34 54 Example 12 Compound 1-12 Compound 3-12 3.80 5.31 65 Reference Example 1 Compound 1-13 ET1 4.00 5.04 10 Comparative Example 1 Compound 1-13 ET2 4.20 5.00 10 Comparative Example 2 HB1 Compound 3-6 4.31 4.91 35 Comparative Example 3 Compound 1-7 ET3 5.05 4.50 5

As shown in Table 1, the organic light emitting device of the embodiment using the compound having a specific dipole moment value of the hole blocking layer material and the electron transport layer material, respectively, compared to the organic light emitting device of the comparative example, excellent organic light emitting device characteristics It can be seen that.

Specifically, the organic light emitting device of Example is Comparative Example 2 employing a compound having a dipole moment value of less than 3.5 in the electron transport layer and Comparative Example 2 employing a compound having a dipole moment value of more than 3 and 2 and the hole blocking layer It can be seen that the organic light emitting device exhibits excellent characteristics in terms of driving voltage, luminous efficiency and lifetime. In general, in view of the trade-off relationship between the luminous efficiency and lifespan of organic light emitting diodes, organic light emitting diodes employing a combination of the compounds of the present invention have significantly improved device characteristics. It means.

1: substrate 2: anode
3: hole transport layer 4: light emitting layer
5: hole blocking layer 6: electron transport layer
7: cathode 8: hole injection layer
9: electron injection layer

Claims (15)

anode;
Hole transport layer;
Light emitting layer;
Hole blocking layer;
Electron transport layer; And
Including a cathode,
The hole blocking layer includes a first compound having a dipole moment of 0 to 2,
The electron transport layer includes a second compound having a dipole moment value of 3.5 to 10,
Organic light emitting device.
The method of claim 1,
The first compound is represented by the following formula (1),
Organic light emitting device:
[Formula 1]

In Chemical Formula 1,
L ₁ to L ₃ are each independently a single bond; Or substituted or unsubstituted C _6-60 arylene,
Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted C _6-60 aryl; Or C _2-60 heteroaryl containing 1 to 3 heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S,
A is a monovalent substituent of the compound represented by the following formula (2),
[Formula 2]

In Chemical Formula 2,
T ₁ is a C _6-20 aromatic ring fused with a neighboring pentagram,
X ₁ is

,

, or

ego,
Y ₁ and Y ₂ are each, independently, hydrogen or deuterium, or together form a single bond, O, S, NR ₅ , CR ₆ R ₇ , or SiR ₈ R ₉ R ₁₀ ,
Z ₁ and Z ₂ are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted C _1-60 alkyl,
R ₁ to R ₁₀ are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted C _6-60 aryl; Or C _2-60 heteroaryl including one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S, or adjacent substituents are bonded to each other to form a C _6-60 spiro ring; C _6-60 aromatic ring; Or a C _2-60 heteroaromatic ring containing at least one N atom,
a1 to a4 are each independently an integer of 0 to 3,
when a1 to a4 are each 2 or more, the structures in the two or more parentheses are the same as or different from each other,
Provided that L ₁ to L ₃ , Ar ₁ , Ar _2, and A are not substituted with cyano.
The method of claim 2,
L ₁ to L ₃ are each independently a single bond, phenylene, biphenylylene, or naphthylene,
Organic light emitting device.
The method of claim 2,
Ar ₁ and Ar ₂ are each independently phenyl, methylphenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, carbazolyl, dibenzofuranyl, dibenzothiophenyl, or pyridinyl,
Organic light emitting device.
The method of claim 2,
A is any one selected from the group consisting of Chemical Formulas 2a to 2k,
Organic light emitting device:

In Chemical Formulas 2a to 2k,
W ₁ is a single bond, O, S, or N (phenyl),
* Represents a position connected to L ₃ of the formula (1).
The method of claim 2,
A is any one selected from the group consisting of
Organic light emitting device:

In the above,
W 'is O or S,
* Represents a position connected to L ₃ of the formula (1).
The method of claim 2,
The first compound is any one selected from the group consisting of
Organic light emitting device:

The method of claim 1,
The second compound is represented by the following formula (3),
Organic light emitting device:
[Formula 3]

In Chemical Formula 3,
L ₄ to L ₆ are each independently a single bond; Or substituted or unsubstituted C _6-60 arylene,
Ar ₃ and Ar ₄ are each independently a substituted or unsubstituted C _6-60 aryl; Or C _2-60 heteroaryl containing 1 to 3 heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S,
B is a monovalent substituent of the compound represented by the following formula (4),
[Formula 4]

In Chemical Formula 4,
T ₂ is a C _6-20 aromatic ring fused with a neighboring pentagram,
X ₂ is

, or

ego,
Y ₃ and Y ₄ are each independently hydrogen, deuterium, or cyano, or together form a single bond, O, S, NQ ₅ , CQ ₆ Q ₇ , or SiQ ₈ Q ₉ Q ₁₀ ,
Q ₁ to Q ₁₀ are each independently hydrogen; heavy hydrogen; Cyano; Substituted or unsubstituted C _6-60 aryl; Or C _2-60 heteroaryl including one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S, or adjacent substituents are bonded to each other to form a C _6-60 spiro ring; C _6-60 aromatic ring; Or a C _2-60 heteroaromatic ring containing at least one N atom,
b1 to b4 are each independently an integer of 0 to 3,
when b1 to b4 are each 2 or more, the structures in the two or more parentheses are the same as or different from each other,
Provided that at least one of L ₄ to L ₆ , Ar ₃ , Ar _4, and B is substituted with cyano.
The method of claim 8,
The second compound is represented by the formula 3A, 3B, 3C, 3D, 3E, or 3F,
Organic light emitting device:
[Formula 3A]

In Chemical Formula 3A,
L ₄ to L ₆ are each independently a single bond; Or C _6-20 arylene unsubstituted or substituted with cyano,
Ar ₃ and Ar ₄ are each independently C _6-20 aryl unsubstituted or substituted with methyl or cyano,
Q ₁ to Q ₃ are each independently hydrogen; heavy hydrogen; Or cyano,
Provided that at least one of L ₄ to L ₆ is C _6-20 arylene substituted with cyano;
At least one of Ar ₃ and Ar ₄ is C _6-20 aryl substituted with cyano; or
At least one of Q ₁ to Q ₃ is cyano,
[Formula 3B]

[Formula 3C]

In Chemical Formulas 3B and 3C,
W ₂ is O, S, NQ ₅ , CQ ₆ Q ₇ , or SiQ ₈ Q ₉ Q ₁₀ ,
L ₄ to L ₆ are each independently a single bond; Or C _6-20 arylene unsubstituted or substituted with cyano,
Ar ₃ and Ar ₄ are each independently C _6-20 aryl unsubstituted or substituted with methyl or cyano,
Q ₁ to Q ₁₀ are each independently hydrogen; heavy hydrogen; Cyano; Or C _6-60 aryl unsubstituted or substituted with cyano,
Provided that at least one of L ₄ to L ₆ is C _6-20 arylene substituted with cyano;
At least one of Ar ₃ and Ar ₄ is C _6-20 aryl substituted with cyano; or
At least one of Q ₁ to Q ₁₀ is cyano or C _6-60 aryl substituted with cyano,
[Formula 3D]

[Formula 3E]

In Chemical Formulas 3D and 3E,
T ₂ is a benzene, naphthalene, or phenanthrene ring fused with a neighboring pentagram;
L ₄ to L ₆ are each independently a single bond; Or C _6-20 arylene unsubstituted or substituted with cyano,
Ar ₃ and Ar ₄ are each independently C _6-20 aryl unsubstituted or substituted with methyl or cyano,
Q ₁ to Q ₄ are each independently hydrogen; heavy hydrogen; Or cyano,
Provided that at least one of L ₄ to L ₆ is C _6-20 arylene substituted with cyano;
At least one of Ar ₃ and Ar ₄ is C _6-20 aryl substituted with cyano; or
At least one of Q ₁ to Q ₄ is cyano,
[Formula 3F]

In Chemical Formula 3F,
L ₄ to L ₆ are each independently a single bond; Or C _6-20 arylene unsubstituted or substituted with cyano,
Ar ₃ and Ar ₄ are each independently C _6-20 aryl unsubstituted or substituted with methyl or cyano,
Q ₁ to Q ₄ , Q ₁₁ and Q ₁₂ are each independently hydrogen; heavy hydrogen; Or cyano,
Provided that at least one of L ₄ to L ₆ is C _6-20 arylene substituted with cyano;
At least one of Ar ₃ and Ar ₄ is C _6-20 aryl substituted with cyano; or
At least one of Q ₁ to Q ₄ , Q ₁₁ and Q ₁₂ is cyano.
The method of claim 8,
L ₄ to L ₆ are each independently a single bond; Phenylene unsubstituted or substituted with cyano; Biphenylylene, unsubstituted or substituted with cyano; Terphenylylene, unsubstituted or substituted with cyano; Or naphthylene unsubstituted or substituted with cyano,
Organic light emitting device.
The method of claim 8,
Ar ₃ and Ar ₄ are each independently phenyl unsubstituted or substituted with cyano; Biphenylyl unsubstituted or substituted with cyano; Or terphenylyl unsubstituted or substituted with cyano; Or 9,9-dimethylfluorene unsubstituted or substituted with cyano,
Organic light emitting device.
The method of claim 8,
B is any one selected from the group consisting of Formulas 4a to 4h,
Organic light emitting device:

In Chemical Formulas 4a to 4h,
W ₂ is O, S, or N (phenyl),
Q ₁ to Q ₄ , Q ₁₁ and Q ₁₂ are each independently hydrogen or cyano,
* 'Represents a position connected to L ₆ of the formula (3).
The method of claim 8,
In Chemical Formula 4a,
Q ₁ to Q ₃ are all hydrogen; Or one of Q ₁ to Q ₃ is cyano, the other is hydrogen,
In Chemical Formulas 4b to 4f and 4h,
Q ₁ to Q ₄ are all hydrogen; Or one of Q ₁ to Q ₄ is cyano, the other is hydrogen,
In Chemical Formula 4g,
Q ₁ to Q ₄ , Q ₁₁ and Q ₁₂ are all hydrogen; Or one of Q ₁ to Q ₄ , Q ₁₁ and Q ₁₂ is cyano, the other is hydrogen,
Organic light emitting device.
The method of claim 8,
B is any one selected from the group consisting of
Organic light emitting device:

In the above,
Q ₁ to Q ₄ , Q ₁₁ and Q ₁₂ are each independently hydrogen or cyano,
* 'Represents a position connected to L ₆ of the formula (3).
The method of claim 8,
The second compound is any one selected from the group consisting of
Organic light emitting device:

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