KR102227968B1 - Organic light emitting device - Google Patents

Abstract

The present invention provides an organic light emitting device.

Description

Organic light emitting device TECHNICAL FIELD

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

In general, the organic light emission phenomenon refers to a phenomenon in which electrical energy is converted into light energy by using an organic material. Organic light-emitting devices using the organic light-emitting phenomenon have a wide viewing angle, excellent contrast, and fast response time, and are excellent in luminance, driving voltage, and response speed characteristics, so many studies are being conducted.

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

Development of new materials for organic materials used in organic light emitting devices as described above is continuously required.

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 above problems, the present invention provides the following organic light emitting device.

The organic light-emitting device according to the present invention,

anode; Hole transport layer; Light-emitting layer; Hole blockage 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 above-described organic light-emitting device may have low driving voltage, high luminous efficiency, and long lifespan characteristics by using a hole blocking layer and an electron transport layer material satisfying a specific dipole moment value.

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 is 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 device comprising the cathode 7 is shown.

Hereinafter, it 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.

In the present specification, the term "substituted or unsubstituted" refers to deuterium; Halogen group; Cyano group; Nitro group; Hydroxy group; Carbonyl group; Ester group; Imide group; Amino group; Phosphine oxide group; Alkoxy group; Aryloxy group; Alkyl thioxy group; Arylthioxy group; Alkyl sulfoxy group; Arylsulfoxy group; Silyl group; Boron group; Alkyl group; Cycloalkyl group; Alkenyl group; Aryl group; Aralkyl group; Aralkenyl group; Alkylaryl group; Alkylamine group; Aralkylamine group; Heteroarylamine group; Arylamine group; Arylphosphine group; Or it means substituted or unsubstituted with one or more substituents selected from the group consisting of a heteroaryl group containing one or more of N, O, and S atoms, or substituted or unsubstituted with two or more substituents connected among the above-exemplified substituents. . For example, "a substituent to which two or more substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group, or may be interpreted as a substituent to which two phenyl groups are connected.

In the present specification, 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 ester group may be substituted with a C1-C25 linear, branched or cyclic alkyl group or an aryl group having 6 to 25 carbon atoms in the oxygen of the ester group. Specifically, it may be a compound of the following structural formula, but is not limited thereto.

In the present specification, the number of carbon atoms of the imide group is not particularly limited, but it 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 specifically includes a trimethyl boron group, a triethyl boron group, a t-butyldimethyl 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 linear or branched, and the number of carbon atoms 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, cycloheptylmethyl, 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 are not limited thereto.

In the present specification, the alkenyl group may be a linear or branched chain, and the number of carbon atoms is not particularly limited, but is preferably 2 to 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 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 are 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 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, or a terphenyl group, but the monocyclic aryl group is not limited thereto. The polycyclic aryl group may be a naphthyl group, an anthracenyl group, a phenanthrenyl group, a pyrenyl group, a perylenyl group, a chrysenyl group, a 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 be bonded to each other to form a spiro structure. When the fluorenyl group is substituted,

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

In the present specification, heteroaryl is a heteroaryl containing one or more of O, N, Si, and S as heterogeneous elements, and the number of carbons 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, acridyl 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 Group, a phenothiazinyl group, a dibenzofuranyl group, and the like, but are not limited thereto.

In the present specification, the aryl group among 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 aforementioned alkyl group. In the present specification, the heteroaryl among the heteroarylamines may be described above for heteroaryl. In the present specification, the alkenyl group of the aralkenyl group is the same as the example of the alkenyl group described above. 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 above-described 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 aryl group or cycloalkyl group described above may be applied except that the hydrocarbon ring is formed by bonding of two substituents. In the present specification, the heterocycle is not a monovalent group, and the description of the above-described heteroaryl may be applied except that the heterocycle is formed by bonding of two substituents.

Meanwhile, in order to improve the efficiency of an organic light-emitting device, a compound having a high dipole moment, that is, a high intramolecular polarity, is used as an electron transport layer material positioned in an electron transport region between a cathode and an emission layer. However, when the electron transport layer including a compound having a high dipole moment contacts the light emitting layer, excitons generated at the interface are 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 that of 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 Prevents the loss of excitons in

Specifically, the first compound included in the hole blocking layer has a dipole moment value of 0 to 2, and 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 more than 2, it cannot function as a hole blocking layer, and excitons are lost at the interface with the emission 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, the formation of excitons may be inhibited, thereby reducing the efficiency of the organic light-emitting device, and when it exceeds 10, a large amount of excitons are formed and lost at the interface with the emission layer, resulting in the organic light-emitting device. Life may be reduced. Accordingly, by using the first compound and the second compound having a dipole moment value in the above-described range for 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 lifespan.

For example, the first compound may have a dipole moment value of more than 0 and less than 2, or 0.1 to less than 2, or 0.3 to 1.9, or 0.5 to 1.9. In addition, 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 can be smoothly transferred to the cathode-electron transport layer-hole blocking layer-luminescent layer. . Therefore, it is necessary that the materials included in the hole blocking layer and the electron transport layer have similar moieties and have a dipole moment in the above-described range, and in order to implement this, the organic light-emitting device of the present invention, as described later, A second compound represented by the following formula (3), which necessarily contains a cyano group, is included in the electron transport layer while including a first compound represented by the following formula (1), which does not contain a cyano group.

As a result, the organic light-emitting device does not have a cyano group, so that the loss of excitons of the light-emitting layer is prevented due to the hole blocking layer exhibiting a low dipole moment value, and at the same time, the density of the electron transport layer according to the compound substituted with the cyano group is increased, so that the cyano group Compared to an organic light-emitting device having a hole blocking layer including a compound substituted with and an electron transport layer not including a compound substituted with a cyano group, it exhibits high efficiency and increased lifespan.

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

[Equation 1]

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

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 preferable so that holes can be smoothly injected into the organic layer. Specific examples of the cathode 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); Combinations of metals and oxides such as ZnO:Al or SnO _{2 :Sb;} Poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), conductive polymers such as polypyrrole and polyaniline, and the like, but are not limited thereto.

It is preferable that the cathode material is a material having a small work function to facilitate electron injection into the organic material layer. Specific examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof; There are multilayered materials such as LiF/Al or LiO ₂ /Al, but are not limited thereto.

In addition, a hole injection layer may be additionally included on the anode. The hole injection layer is made of a hole injection material, and the hole injection material has the ability to transport holes, and thus has a hole injection effect at the anode, an excellent hole injection effect for the light emitting layer or the light emitting material, and excitons generated in the light emitting layer A compound that prevents migration to the electron injection layer or the electron injection material and has excellent thin film formation ability is preferable.

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

Hole transport layer

The hole transport layer used in the present invention is a layer that receives holes from the anode or the hole injection layer formed on the anode and transports holes to the emission layer.It can be transferred to the emission layer by transporting holes from the anode or the hole injection layer as a hole transport material. A material with high mobility for holes is suitable as a material.

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

Light emitting layer

The light-emitting material included in the light-emitting layer is a material capable of emitting light in the visible light region by transporting and combining holes and electrons from the hole transport layer and the electron transport layer, and a material having good quantum efficiency against fluorescence or phosphorescence is preferable.

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

The emission layer may include a host material and a dopant material. Host materials include condensed aromatic ring derivatives or heterocyclic-containing compounds. Specifically, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, and fluoranthene compounds, and heterocycle-containing compounds include carbazole derivatives, dibenzofuran derivatives, ladder type Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.

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

Hole bottom

The hole blocking layer is formed on the emission layer, and specifically, the hole blocking layer is provided in contact with the emission layer to prevent excessive movement of holes, thereby increasing the probability of hole-electron bonding, thereby improving the efficiency of the organic light-emitting device. It means the layer to do. In particular, in the present invention, a 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. Does not.

The first compound is represented by the following formula (1):

[Formula 1]

In Formula 1,

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

Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted C _6-60 aryl; _{Or substituted or unsubstituted C 2-60} heteroaryl containing 1 to 3 heteroatoms selected from the group consisting of 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 pentagonal ring,

,

, 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 ,

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

R ₁ to R ₉ are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted C _6-60 aryl; _{Or a substituted or unsubstituted C 2-60} heteroaryl containing one or more heteroatoms selected from the group consisting of N, O and S _{, or a C 6-60} spiro ring by bonding of adjacent substituents to each other; C _6-60 aromatic ring; Or it may form _{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,

However, L ₁ to L ₃ , Ar ₁ , Ar ₂ and A are not substituted with cyano.

In this case, the _{meaning of'L 1} to L ₃ , Ar ₁ , Ar ₂ and A is not substituted with cyano _{' in Formula 1 means that when L 1} to L ₃ are each C _6-60 arylene, It means that _{the substituent of Ar 1,} the substituent of Ar ₂ , and the substituent of A (R ₁ to R ₁₂ ) are not all cyano groups.

In Formula 1, L ₁ to L ₃ may each independently be 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 containing 1 or 2 heteroatoms selected from the group consisting of N, O and S unsubstituted or substituted with 1 to 3 substituents selected from the group consisting of methyl, phenyl and pyridinyl May be _{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 ₉ are each independently hydrogen; heavy hydrogen; C _6-60 aryl; _{Or C 2-60} heteroaryl containing one or more heteroatoms selected from the group consisting of N, O and S; R ₅ is combined with an adjacent substituent to form an indole or carbazole ring; Alternatively, R ₆ and R ₇ may be bonded to each other to form fluorene and a spiro ring. In this case, forming a spiro structure means having a structure in which one carbon is connected by a contact point.

In addition, A may be represented by the following formulas 2-1 to 2-9, depending on the structure of _{X 1:}

In 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 pentagonal ring,

W ₁ is a single bond, O, S, or NR ₅ ,

Here, R ₅ is C _6-20 aryl, or may be combined 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 in} Formula 1.

In 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. Can be formed and condensed with an adjacent ring,

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 the following 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 in Formula 1} Show. 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:

Above,

W'is O or S,

* Represents a position connected to _{L 3 in} Formula 1.

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

On the other hand, the compound represented by Formula 1 may be prepared by a manufacturing method such as the following Scheme 1 as an example.

[Scheme 1]

In Reaction Scheme 1, _{descriptions of L 1} to L ₃ , Ar ₁ , Ar ₂ and A are as defined in Chemical Formula 1, and X is halogen, preferably bromo or chloro. The reaction is a Suzuki coupling reaction, preferably carried out in the presence of a palladium catalyst, and the reactor for the Suzuki coupling reaction can be changed 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 and 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 the material of the electron transport layer, and at least one of _{L 4} to L ₆ , Ar ₃ , Ar _{4 and B in Chemical Formula 3 is cyano.} Is substituted.

The second compound is represented by the following formula (3):

[Formula 3]

In Chemical Formula 3,

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

Ar ₃ and Ar ₄ are each independently a substituted or unsubstituted C _6-60 aryl; _{Or substituted or unsubstituted C 2-60} heteroaryl containing 1 to 3 heteroatoms selected from the group consisting of 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 pentagonal ring,

, 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 ₁ to Q ₉ are each independently hydrogen; heavy hydrogen; Cyano; Substituted or unsubstituted C _6-60 aryl; _{Or a substituted or unsubstituted C 2-60} heteroaryl containing one or more heteroatoms selected from the group consisting of N, O and S _{, or a C 6-60} spiro ring by bonding of adjacent substituents to each other; C _6-60 aromatic ring; Or it may form _{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,

However, _{at least one of L 4} to L ₆ , Ar ₃ , Ar ₄ and B is substituted with cyano.

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

Specifically, in the case where L ₄ to L _{6 in} Formula 3 is C _6-60 arylene, one to _{3 of the substituents Ar 3,} the substituents of Ar ₄ , and the substituents of B (Q ₁ to Q ₁₂ ) Dogs can be cyano groups.

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 in} Formula 3 are each C _6-60 arylene, one of the substituents Ar _3, the substituents of Ar ₄ , and the substituents of B (Q ₁ to Q ₁₂ ) or Two may be cyano groups.

In addition, in the definition of a substituent in the present specification, the term "substituted with cyano" means that at least one hydrogen, preferably one or two hydrogens, among the hydrogens included in the substituent has been substituted with a cyano group.

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

Organic Light-Emitting Element:

[Formula 3A]

In 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, unsubstituted or C _6-20 aryl 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]

[Chemical Formula 3C]

In Formulas 3B and 3C,

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

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, unsubstituted or C _6-20 aryl substituted with methyl or cyano,

Q ₁ to Q ₉ 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 _{9 is cyano or C 6-60} aryl substituted with cyano,

[Chemical Formula 3D]

[Chemical Formula 3E]

In Chemical Formulas 3D and 3E,

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

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, unsubstituted or C _6-20 aryl 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,}

[Chemical Formula 3F]

In 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, unsubstituted or C _6-20 aryl 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 definition of a substituent in the present specification, the term "unsubstituted or substituted with methyl or cyano C _6-20 aryl" refers to 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 it may be 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 it may be unsubstituted or naphthylene substituted with cyano.

In addition, Ar ₃ and Ar ₄ may each independently be an unsubstituted or C _6-20 aryl 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 it may be 9,9-dimethylfluorene unsubstituted or substituted with cyano.

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

In addition, in Formula 4, Q ₁ to Q ₉ 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 bonded to an adjacent substituent to indole or Form a carbazole ring; Alternatively, Q ₆ and Q ₇ may be bonded to each other to form a spiro ring with fluorene.

In addition, Q ₁ to Q ₄ , Q ₁₁ and Q ₁₂ may each independently be hydrogen or cyano. In addition, Q ₅ to Q ₉ are each independently hydrogen; heavy hydrogen; Cyano; _{C 6-20} aryl unsubstituted or substituted with cyano; Or it may be _{a 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 Formulas 4-1 to 4-8, depending on the structure of _{X 2:}

In Formulas 4-1 to 4-8,

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

W ₂ is a single bond, O, S, or NQ ₅ ,

Q ₅ is C _6-20 aryl, or may be combined 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 in} Chemical Formula 3.

Specifically, in 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 each independently be hydrogen or cyano.

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

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

In Formula 4g, Q ₁ to Q ₄ , Q ₁₁ and Q ₁₂ are all hydrogen; Alternatively, one of Q ₁ to Q ₄ , Q ₁₁ and Q ₁₂ may be cyano, and the rest 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 in Formula 3 above.}

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

On the other hand, the compound represented by Formula 3 may be prepared by a manufacturing method as shown in Scheme 2 below as an example.

[Scheme 2]

In Reaction Scheme 2, _{descriptions of L 4} to L ₆ , Ar ₃ , Ar ₄ and B are as defined in Chemical Formula 3, and X is halogen, preferably bromo or chloro. The reaction is a Suzuki coupling reaction, preferably carried out in the presence of a palladium catalyst, and the reactor for the Suzuki coupling reaction can be changed 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 the electrode, has an ability to transport electrons, has an electron injection effect from the cathode, an excellent electron injection effect for 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 include LiF, NaCl, CsF, Li ₂ O, BaO, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, Derivatives thereof, such as perylenetetracarboxylic acid, preorenylidene methane, anthrone, and the like, metal complex compounds, and nitrogen-containing 5-membered ring derivatives, but are not limited thereto.

Organic light emitting element

The structure of the organic light emitting device according to the present invention is illustrated in FIG. 1. 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 is 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 device comprising the cathode 7 is shown. 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 configurations. At this time, using a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation, the anode is formed by depositing a metal or a conductive metal oxide or an alloy thereof on the substrate. And, after forming each of the above-described layers thereon, 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 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 by a solution coating method as well as a vacuum deposition method of a host and a dopant. Here, the solution coating method refers to spin coating, dip coating, doctor blading, inkjet printing, screen printing, spray method, roll coating, and the like, but is not limited thereto.

In addition to such a method, an organic light emitting device may be manufactured by sequentially depositing an organic material layer and an anode material from a cathode material on a substrate (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-sided emission type depending on the material used.

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

[Preparation of the second compound]

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

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

MS:[M+H] ⁺ = 651

Manufacturing example 2: Preparation of compound 3-2

The compound A2 (10 g, 21.2 mmol) and the 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 refluxing for 5 hours. After cooling to room temperature, the resulting solid was filtered and recrystallized with chloroform and ethanol to prepare compound 3-2 (10.5 g, yield 71%).

MS:[M+H] ⁺ = 701

Manufacturing example 3: Preparation of compound 3-3

The compound A3 (10 g, 24.3 mmol) and the 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 refluxing for 5 hours. After cooling to room temperature, the resulting solid was filtered and recrystallized with chloroform and ethanol to prepare the compound 3-3 (12.6 g, yield 78%).

MS:[M+H] ⁺ = 665

Manufacturing example 4: Preparation of compound 3-4

The compound A4 (10 g, 22.9 mmol) and the 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 refluxing for 5 hours. After cooling to room temperature, the resulting solid was filtered and recrystallized with chloroform and ethanol to prepare the compound 3-4 (10.4 g, yield 68%).

MS:[M+H] ⁺ = 665

Manufacturing example 5: Preparation of compound 3-5

The compound A5 (10 g, 17.9 mmol) and the 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 refluxing for 5 hours. After cooling to room temperature, the resulting solid was filtered and recrystallized with chloroform and ethanol to prepare the compound 3-5 (9.9 g, yield 62%).

MS:[M+H] ⁺ = 890

Manufacturing example 6: Preparation of compound 3-6

The compound A3 (10 g, 24.3 mmol) and the 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 refluxing for 5 hours. After cooling to room temperature, the resulting solid was filtered and recrystallized with chloroform and ethanol to prepare the compound 3-6 (12.9 g, yield 80%).

MS:[M+H] ⁺ = 665

Manufacturing 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 in Preparation Example 3-1, and Compound B6 was used instead of Compound B1.

MS:[M+H] ⁺ = 650

Manufacturing 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 in Preparation Example 3-1, and Compound B7 was used instead of Compound B1.

MS:[M+H] ⁺ = 741

Manufacturing example 9: Preparation of compound 3-9

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

MS:[M+H] ⁺ = 651

Manufacturing 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 in Preparation Example 3-1, and Compound B6 was used instead of Compound B1.

MS:[M+H] ⁺ = 665

Manufacturing 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 in Preparation Example 3-1, and Compound B7 was used instead of Compound B1.

MS:[M+H] ⁺ = 665

Manufacturing 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 in Preparation Example 3-1, and Compound B7 was used instead of Compound B1.

MS:[M+H] ⁺ = 741

[Preparation of the first compound]

Manufacturing 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 in Preparation Example 3-1, and Compound C1 was used instead of Compound B1.

MS:[M+H] ⁺ = 729

Manufacturing 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 in Preparation Example 3-1, and Compound C2 was used instead of Compound B1.

MS:[M+H] ⁺ = 654

Manufacturing 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 in Preparation Example 3-1, and Compound C3 was used instead of Compound B1.

MS:[M+H] ⁺ = 640

Manufacturing 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 in Preparation Example 3-1, and Compound C4 was used instead of Compound B1.

MS:[M+H] ⁺ = 592

Manufacturing 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 in Preparation Example 3-1, and Compound C5 was used instead of Compound B1.

MS:[M+H] ⁺ = 726

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

Compound 1 using the same method 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

Manufacturing 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 in Preparation Example 3-1, and Compound C7 was used instead of Compound B1.

MS:[M+H] ⁺ = 716

Manufacturing 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 in Preparation Example 3-1, and Compound C8 was used instead of Compound B1.

MS:[M+H] ⁺ = 713

Manufacturing example 1-9: Preparation of compound 1-9

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

MS:[M+H] ⁺ = 536

Manufacturing 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 in Preparation Example 3-1, and Compound C10 was used instead of Compound B1.

MS:[M+H] ⁺ = 650

Manufacturing 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 in Preparation Example 3-1, and Compound C11 was used instead of Compound B1.

MS:[M+H] ⁺ = 639

Manufacturing 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 in Preparation Example 3-1, and Compound C12 was used instead of Compound B1.

MS:[M+H] ⁺ = 713

Manufacturing example 1-13: Preparation of compound 1-13

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

MS:[M+H] ⁺ = 578

Example One

A glass substrate (corning 7059 glass) coated with a thin film of ITO (indium tin oxide) having a thickness of 1000Å was placed in distilled water in which a dispersant was dissolved and washed with ultrasonic waves. The detergent was manufactured by Fischer Co., and the distilled water was Millipore Co. Distilled water filtered secondarily with the product's filter was used. After washing the ITO for 30 minutes, ultrasonic washing was performed for 10 minutes by repeating twice with distilled water. After washing with distilled water, ultrasonic washing was performed in the order of isopropyl alcohol, acetone, and methanol, followed by drying.

On the prepared ITO transparent electrode, hexanitrile hexaazatriphenylene (HATCN) was thermally vacuum deposited to a thickness of 500 Å to form a hole injection layer. HT1 (400 Å), which is a material for transporting holes, was vacuum deposited thereon to form a hole transport layer.

A light emitting layer was formed by vacuum depositing a host H1 and a dopant D1 compound to a thickness of 300 Å on the hole transport layer.

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

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 Å on the electron transport layer to form an electron injection layer and a cathode.

In the above process, the deposition rate of organic materials was maintained at 0.4 to 0.7 Å/sec, the deposition rate of lithium fluoride at the negative electrode was 0.3 Å/sec, and the deposition rate of aluminum was 2 Å/sec, and the vacuum degree during deposition was 2 x10 ^-7. By maintaining ~ 5 x10 ^-6 torr, an organic light emitting device was manufactured.

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 material, 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 example are summarized as follows.

The electron transport layer material compounds 3-1 to 3-12 used in the above example are summarized as follows.

The hole blocking layer material HB1, the hole transport layer material ET1, ET2, and ET3 used in the Reference Examples and Comparative Examples are summarized as follows.

At this time, values of dipole moments of the compounds used in the Examples and Comparative Examples are shown in Table 1 below.

Hole bottom 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 device prepared in the above Examples and Comparative Examples, the driving voltage and luminous efficiency at a current density of ^{10 mA/cm 2} , and a time to become 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 bottom
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 Example using a compound having a dipole moment value in a specific range as a hole blocking layer material and an electron transport layer material, respectively, compared to the organic light-emitting device of Comparative Example, has excellent organic light-emitting device characteristics. You can see

Specifically, the organic light-emitting device of the embodiment, Comparative Examples 1 and 3 in which a compound having a dipole moment value of less than 3.5 was employed in the electron transport layer, and Comparative Example 2 in which a compound having a dipole moment value exceeding 2 was employed in the hole blocking layer. It can be seen that compared to the organic light emitting device of, it exhibits excellent characteristics in terms of driving voltage, luminous efficiency, and lifetime. Considering that the luminous efficiency and lifetime characteristics of the organic light-emitting device generally have a trade-off relationship with each other, the organic light-emitting device employing a combination of the compounds of the present invention has significantly improved device characteristics compared to the comparative example device. Means to represent.

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 blockage 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 of 3.5 to 10,
The second compound is represented by the following formula (3),
Organic Light-Emitting Element:
[Formula 3]

In Chemical Formula 3,
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, unsubstituted or C _6-20 aryl substituted with methyl or cyano,
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 pentagonal ring,
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 ₁ to Q ₉ are each independently hydrogen; heavy hydrogen; Cyano; Substituted or unsubstituted C _6-60 aryl; _{Or a substituted or unsubstituted C 2-60} heteroaryl containing one or more heteroatoms selected from the group consisting of N, O and S _{, or a C 6-60} spiro ring by bonding of adjacent substituents to each other; C _6-60 aromatic ring; Or it may form _{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 or different,
However, _{at least one of L 4} to L ₆ , Ar ₃ , Ar ₄ and B is substituted with cyano.
The method of claim 1,
The first compound is represented by the following formula (1),
Organic Light-Emitting Element:
[Formula 1]

In Formula 1,
L ₁ to L ₃ are each independently a single bond; Or a substituted or unsubstituted C _6-60 arylene,
Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted C _6-60 aryl; _{Or substituted or unsubstituted C 2-60} heteroaryl containing 1 to 3 heteroatoms selected from the group consisting of 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 pentagonal ring,
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 ,
Z ₁ and Z ₂ are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted C _1-60 alkyl,
R ₁ to R ₉ are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted C _6-60 aryl; _{Or a substituted or unsubstituted C 2-60} heteroaryl containing one or more heteroatoms selected from the group consisting of N, O and S _{, or a C 6-60} spiro ring by bonding of adjacent substituents to each other; C _6-60 aromatic ring; Or it may form _{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,
However, 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 the following formulas 2a to 2k,
Organic Light-Emitting Element:

In Formulas 2a to 2k,
W ₁ is a single bond, O, S, or N (phenyl),
* Represents a position connected to _{L 3 in} Formula 1.
The method of claim 2,
A is any one selected from the group consisting of,
Organic Light-Emitting Element:

Above,
W'is O or S,
* Represents a position connected to _{L 3 in} Formula 1.
The method of claim 2,
The first compound is any one selected from the group consisting of,
Organic Light-Emitting Element:

.
delete The method of claim 1,
The second compound is represented by the following formula 3A, 3B, 3C, 3D, 3E, or 3F,
Organic Light-Emitting Element:
[Formula 3A]

In Formula 3A,
L ₄ to L ₆ , Ar ₃ and Ar ₄ are as defined in claim 1,
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]

[Chemical Formula 3C]

In Formulas 3B and 3C,
W ₂ is O, S, NQ ₅ , CQ ₆ Q ₇ , or SiQ ₈ Q ₉ ,
L ₄ to L ₆ , Ar ₃ and Ar ₄ are as defined in claim 1,
Q ₁ to Q ₉ 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 _{9 is cyano or C 6-60} aryl substituted with cyano,
[Chemical Formula 3D]

[Chemical Formula 3E]

In Chemical Formulas 3D and 3E,
T ₂ is a benzene, naphthalene, or phenanthrene ring fused with a neighboring pentagonal ring,
L ₄ to L ₆ , Ar ₃ and Ar ₄ are as defined in claim 1,
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,}
[Chemical Formula 3F]

In Formula 3F,
L ₄ to L ₆ , Ar ₃ and Ar ₄ are as defined in claim 1,
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 1,
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 1,
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 1,
B is any one selected from the group consisting of the following formulas 4a to 4h,
Organic Light-Emitting Element:

In 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 in} Chemical Formula 3.
The method of claim 12,
In Formula 4a,
Q ₁ to Q ₃ are all hydrogen; Or one of Q ₁ to Q ₃ is cyano, and 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, and 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 is cyano, and the rest is hydrogen,
Organic light emitting device.
The method of claim 1,
B is any one selected from the group consisting of,
Organic Light-Emitting Element:

Above,
Q ₁ to Q ₄ , Q ₁₁ and Q ₁₂ are each independently hydrogen or cyano,
*'represents a position connected to _{L 6 in} Chemical Formula 3.
The method of claim 1,
The second compound is any one selected from the group consisting of,
Organic Light-Emitting Element:

.

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