KR102290840B1 - Organic light emitting device - Google Patents

Abstract

The present invention provides an organic light emitting device.

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 lifetime.

In general, the organic light emitting phenomenon refers to a phenomenon in which electric energy is converted 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, and excellent luminance, driving voltage, and response speed characteristics, and thus 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 layer is often formed of a multi-layered structure composed of different materials in order to increase the efficiency and stability of the organic light-emitting device, and may include, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like. In the structure of the organic light emitting device, when a voltage is applied between the two electrodes, holes are injected into the organic material layer from the anode and electrons from the cathode are injected into the organic material layer. When the injected holes and electrons meet, excitons are formed, and the excitons When it falls back to the ground state, it lights up.

The 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 lifetime.

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,

cathode,

a light emitting layer between the anode and the cathode; and

An electron transport layer between the cathode and the light emitting layer,

The electron transport layer includes a compound represented by the following formula (1) and a metal complex compound:

[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, 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 represented by the following formula 2 or 3,

[Formula 2]

[Formula 3]

In Formula 2 or 3,

W is O, S, CR ₉ R ₁₀ , or SiR ₁₁ R ₁₂ ,

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

R ₁ to R ₈ are each independently hydrogen; heavy hydrogen; or cyano, or adjacent R ₆ and R ₇ may combine with each other to form a spiro ring structure,

R ₉ to R ₁₂ are each independently hydrogen; heavy hydrogen; cyano; 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,

a1 is an integer from 0 to 3,

a2 to a6 and a8 are each independently an integer of 0 to 4,

a7 is an integer from 0 to 5;

When a1 to a8 are each 2 or more, the structures in the two or more parentheses are the same as or different from each other,

* represents a position connected to _{L 3} of Formula 1,

However, _{at least one of L 1} to L ₃ , Ar ₁ , Ar ₂ and A is substituted with cyano.

The above-described organic light emitting device uses the compound represented by Chemical Formula 1 and the metal complex compound to be described later as a material of the electron transport layer at the same time, so that the change in efficiency according to the change in current density is small and the change in color according to the driving environment is small, so a panel to which the same is applied The defect rate can be significantly reduced.

FIG. 1 shows an example of an organic light emitting device including a substrate 1 , an anode 2 , a light emitting layer 3 , an electron transport layer 4 , and a cathode 5 .
2 shows a substrate 1, an anode 2, a hole injection layer 6, a hole transport layer 7, a light emitting layer 3, an electron transport layer 4, an electron injection layer 8 and a cathode 5. An example of an organic light emitting device is shown.
3 is a graph showing the comparison of the efficiency graphs according to the current density of the organic light emitting diodes of Examples 1-15 and Examples 2-15.
4 is a graph showing the comparison of the efficiency graphs according to the current density of the organic light emitting diodes of Comparative Examples 1-4 and Examples 2-4.

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

는 다른 치환기에 연결되는 결합을 의미하고, 단일 결합은 L₁ 내지 L₃로 표시되는 부분에 별도의 원자가 존재하지 않은 경우를 의미한다.In this specification,

refers to a bond connected to another substituent, and a single bond refers to a case in which a separate atom is not present in the portion represented by _{L 1} to L _{3 .}

As used herein, the term "substituted or unsubstituted" refers to deuterium; halogen group; cyano group; nitro group; hydroxyl group; carbonyl group; ester group; imid; amino group; phosphine oxide group; alkoxy group; aryloxy group; alkyl thiooxy group; arylthioxy group; an alkyl sulfoxy group; arylsulfoxy group; silyl group; boron group; an alkyl group; cycloalkyl group; alkenyl group; aryl group; aralkyl group; aralkenyl group; an alkylaryl group; an alkylamine group; an aralkylamine group; heteroarylamine group; arylamine group; an arylphosphine group; or N, O, and S atoms are substituted or unsubstituted with one or more substituents selected from the group consisting of a heteroaryl group containing one or more atoms, or substituted or unsubstituted with two or more substituents connected to the above-exemplified substituents . For example, "a substituent in which two or more substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group, and may be interpreted as a substituent in which two phenyl groups are connected.

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

In the present specification, the number of carbon atoms of the imide group is not particularly limited, but it is preferably from 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 specifically includes a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, a 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, a trimethylboron group, a triethylboron group, a t-butyldimethylboron group, a triphenylboron group, a 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, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to an exemplary embodiment, the number of carbon atoms in the alkyl group is 1 to 20. 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 are not limited thereto.

In the present specification, the alkenyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to an exemplary embodiment, the carbon number of the alkenyl group is 2 to 20. According to another exemplary embodiment, the carbon number of the alkenyl group is 2 to 10. 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 carbon number of the cycloalkyl group is 3 to 20. According to another exemplary embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specifically, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3, 4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like, but is not limited thereto.

In the present specification, the aryl group is not particularly limited, but 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 carbon number of the aryl group is 6 to 30. According to an exemplary embodiment, the carbon number of the aryl group is 6 to 20. The aryl group may be a monocyclic aryl group, such as a phenyl group, a biphenyl group, or a terphenyl group, but is not limited thereto. The polycyclic aryl group may be a naphthyl group, an anthracenyl group, a phenanthryl 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,

etc. can be However, the present invention is not limited thereto.

In the present specification, heteroaryl is a heteroaryl containing at least one of O, N, Si and S as a heterogeneous element, and the number of carbon atoms is not particularly limited, but it is preferably from 2 to 60 carbon atoms. Examples of heteroaryl include a thiophene group, a furan group, a pyrrole group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a triazole group, a pyridyl group, a bipyridyl group, a pyrimidyl group, a triazine group, an acridyl group, Pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyridopyrimidinyl group, pyridopyrazinyl group, pyrazinopyrazinyl 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 group, phenothiazinyl group, and dibenzofuranyl group, but is not limited thereto.

In the present specification, the aryl group in the aralkyl group, the aralkenyl group, the alkylaryl group, and the 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 above-described alkyl group. In the present specification, as for heteroaryl among heteroarylamines, the description regarding heteroaryl described above may be applied. In the present specification, the alkenyl group among the aralkenyl groups is the same as the above-described examples of the alkenyl group. In the present specification, the description of the above-described aryl group may be applied except that arylene is a divalent group. In the present specification, the description of heteroaryl described above may be applied, except that heteroarylene is a divalent group. In the present specification, the hydrocarbon ring is not a monovalent group, and the description of the above-described aryl group or cycloalkyl group may be applied, except that it is formed by combining 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 it is formed by combining two substituents.

On the other hand, the organic light emitting device according to the present invention includes the compound represented by Formula 1 and the metal complex compound at the same time in the electron transport layer located between the cathode and the light emitting layer, so that the compound represented by Formula 1 and the metal complex have a low driving voltage. The difference in power efficiency according to the mixing ratio of the compound is small.

Such an organic light emitting device may be implemented by using a compound having a specific structure substituted with one or more cyano groups as a material for the electron transport layer of the organic light emitting device, which will be described in detail below.

positive and negative

As the anode material, a material having a large work function is generally preferred so that holes can be smoothly injected into the organic material layer. Specific examples of the anode material include metals such as vanadium, chromium, copper, zinc, 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;} conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene](PEDOT), polypyrrole, and polyaniline, but are not limited thereto.

The cathode material is preferably a material having a small work function to facilitate electron injection into the organic material layer. Specific examples of the anode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead, or alloys thereof; and a multilayer structure material such as LiF/Al or LiO ₂ /Al, but is 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, so it has a hole injection effect at the anode, an excellent hole injection effect on the light emitting layer or the light emitting material, and the excitons generated in the light emitting layer A compound which prevents movement to the electron injection layer or the electron injection material and is excellent in the ability to form a thin film is preferred.

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 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, and perylene. organic materials, anthraquinones, polyaniline and polythiophene-based conductive polymers, and the like, 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 hole injection layer formed on the anode or the anode and transports them to the light emitting layer. As a material with high hole mobility, it is suitable.

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

light emitting layer

The light emitting material included in the light emitting layer is a material capable of emitting light in the visible ray region by receiving and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, and a material having good quantum efficiency for fluorescence or phosphorescence is preferable. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq ₃ ); carbazole-based compounds; dimerized styryl compounds; BAlq; 10-hydroxybenzo quinoline-metal compounds; compounds of the benzoxazole, benzthiazole and benzimidazole series; Poly(p-phenylenevinylene) (PPV)-based polymers; spiro compounds; polyfluorene, rubrene, and the like, but is not limited thereto.

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

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

electron transport layer

The organic light emitting diode according to the present invention may include an electron transport layer between the light emitting layer and the electron injection layer. The electron transport layer is a layer that receives electrons from the electron injection layer and transports them to the light emitting layer. do.

In particular, in the present invention, the compound represented by Formula 1 having at least one cyano group and the metal complex compound are simultaneously used as a material for the electron transport layer.

In this case, the meaning that 'at least one of _{L 1} to L ₃ , Ar ₁ , Ar _{2 and A is substituted with cyano' in Formula 1 means a substituent of L 1} , a substituent of L ₂ , a substituent of L ₃ , Ar ₁ It means that at least one of the substituents of , the substituents of Ar _{2 and} the substituents of A (R ₁ to R ₁₂ ) is a cyano group. In this case, the _{meaning that L 1} to L ₃ is substituted with a cyano group It means that L ₁ to L ₃ are C _6-60 arylene.

Since the compound represented by Formula 1 having such a cyano group is included in the electron transport layer, an organic light emitting device satisfying Equation 1 may be implemented.

_{Specifically, one to three} of the substituents of L 1 in Formula 1, the substituents of L _{2 ,} the substituents of L _{3 ,} the substituents of Ar _{1 ,} the substituents of Ar _{2 and} the substituents of A (R ₁ to R ₁₂ ) are cyano. It could be anger.

Preferably, one of L ₁ to L ₃ , Ar ₁ , Ar ₂ and A is substituted with cyano. In other words, one or _{two of the substituents of L 1} in Formula 1, the substituents of L _{2 ,} the substituents of L _{3 ,} the substituents of Ar _{1 ,} the substituents of Ar _{2 and} the substituents of A (R ₁ to R ₁₂ ) are cyan It could be anger.

Also, in the present specification, the term "substituted with cyano" in the definition of a substituent means that one or more hydrogens, preferably one or two hydrogens, among hydrogens included in the substituent are substituted with a cyano group.

The compound represented by Formula 1 may be represented by Formula 1A, 1B, or 1C below:

[Formula 1A]

In Formula 1A,

L ₁ to L ₃ are each independently, a single bond; _{or C 6-20} arylene unsubstituted or substituted with cyano;

Ar ₁ and Ar _{2 are each independently C 6-20} aryl unsubstituted or substituted with methyl or cyano;

W is O or S;

R ₁ to R ₄ are each independently hydrogen; heavy hydrogen; or cyano;

provided that at least one of _{L 1} to L _{3 is C 6-20} arylene substituted with cyano;

at least one of Ar ₁ and Ar _{2 is C 6-20} aryl substituted with cyano; or

At least one of R ₁ to R _{4 is cyano,}

[Formula 1B]

In Formula 1B,

L ₁ to L ₃ are each independently, a single bond; _{or C 6-20} arylene unsubstituted or substituted with cyano;

Ar ₁ and Ar _{2 are each independently C 6-20} aryl unsubstituted or substituted with methyl or cyano;

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

R ₅ to R ₈ are each independently hydrogen; heavy hydrogen; or cyano;

provided that at least one of _{L 1} to L _{3 is C 6-20} arylene substituted with cyano;

at least one of Ar ₁ and Ar _{2 is C 6-20} aryl substituted with cyano; or

At least one of R ₁ to R _{4 is cyano,}

[Formula 1C]

In Formula 1C,

L ₁ to L ₃ are each independently, a single bond; _{or C 6-20} arylene unsubstituted or substituted with cyano;

Ar ₁ and Ar _{2 are each independently C 6-20} aryl unsubstituted or substituted with methyl or cyano;

R ₅ to R ₈ , R ₆ ′ and R ₇ ′ are each independently hydrogen; heavy hydrogen; or cyano;

provided that at least one of _{L 1} to L _{3 is C 6-20} arylene substituted with cyano;

at least one of Ar ₁ and Ar _{2 is C 6-20} aryl substituted with cyano; or

At least one of R ₅ to R ₈ , R ₆ ′ and R _{7 ′ 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" includes 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 _{One To} L ₃ Each independently, a single bond; substituted or unsubstituted phenylene; substituted or unsubstituted biphenylrylene; substituted or unsubstituted terphenylrylene; Or it may be a substituted or unsubstituted naphthylene.

Specifically, for example, L _{One To} L ₃ Each independently, a single bond; phenylene unsubstituted or substituted with cyano; unsubstituted or cyano-substituted biphenylrylene; or unsubstituted or cyano-substituted terphenylrylene.

Specifically, for example, L _{One To} L ₃ Each independently, a single bond; phenylene unsubstituted or substituted with one cyano; or biphenylrylene unsubstituted or substituted with one cyano group.

In addition, Ar ₁ and Ar _{2 may each independently be C 6-20} aryl unsubstituted or substituted with methyl or cyano.

For example, Ar ₁ and Ar ₂ are each independently selected from phenyl unsubstituted or substituted with cyano; biphenylyl unsubstituted or substituted with cyano; or terphenylyl unsubstituted or substituted with cyano; Or it may be unsubstituted or cyano-substituted 9,9-dimethylfluorene.

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 1 or 2 cyano; or terphenylyl unsubstituted or substituted with 1 or 2 cyano; or 9,9-dimethylfluorene unsubstituted or substituted with one or two cyano groups.

In addition, in Formula 2, W may be O or S.

In Formula 2 or 3, R ₁ to R ₈ may each independently be hydrogen or cyano. In addition, R ₉ to R ₁₂ 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 comprising 1 to 3 heteroatoms selected from the group consisting of N, O and S unsubstituted or substituted with cyano. For example, R ₉ to R ₁₂ may each independently be hydrogen or cyano.

In this case, a1 to a8 mean the number of _{R 1} to R _{8 , respectively.} When a1 to a8 are each 2 or more, two or more R ₁ to R ₈ may be the same as or different from each other. For example, a1 to a8 may each independently be 0 or 1.

In addition, A represented by Formula 3 may be represented by the following Formulas 3-1 to 3-10 depending on T. When T is a benzene ring, it can be represented by Formula 3-1, when T is a naphthalene ring, it can be represented by Formulas 3-2 to 3-4, and when T is a phenanthrene ring, it can be represented by Formulas 3-5 to 3-10 have.

In Formulas 3-1 to 3-10, R ₅ to R ₈ and a5 to a8 are as defined in Formula 3, and * represents a position connected to _{L 3 of Formula 1 above.}

In addition, A represented by Formula 3 _{may have a structure in which adjacent R 6} and R ₇ are bonded to each other to form a spiro ring structure, in which another compound structure and one carbon are connected by a contact point. Specifically, adjacent R ₆ and R ₇ of Formula 3 may combine with each other to form a spiro ring structure in which a fluorene structure and one carbon are connected as a contact point, which may be represented by Formula 3-11.

In Formula 3-11, R ₅ to R ₈ and a5 to a8 are as defined in Formula 3 above, and R ₆ ', R ₇ ', a6' and a7' are R ₆ , R ₇ , a6 and a7, respectively. Referring to the description, * represents a position connected to _{L 3 of Formula 1 above.}

Specifically, A may be any one selected from the group consisting of the following formulas 4a to 4e:

In Formulas 4a to 4e,

W is O or S;

R ₁ to R ₈ are as defined in Formulas 2 and 3,

R ₆ ' and R ₇ ' are as defined for _{R 6} and R ₇ in claim 1, respectively,

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

More specifically, in Formulas 4a to 4e, R ₁ to R ₈ , R ₆ ′ and R ₇ ′ may each independently be hydrogen or cyano.

For example, in Formula 4a, R ₁ to R ₄ are hydrogen; or one of R ₁ to R ₄ is cyano, the other is hydrogen,

In Formulas 4b to 4d, R ₅ to R ₈ are hydrogen; or one of R ₅ to R ₈ is cyano, the other is hydrogen,

In Formula 4e, R ₅ to R ₈ , R ₆ ′ and R ₇ ′ are hydrogen; Alternatively, one of R ₅ to R ₈ , R ₆ ′ and R ₇ ′ may be cyano, and the other may be hydrogen.

Meanwhile, the compound represented by Formula 1 may be any one selected from the group consisting of the following Formulas 1-1 to 1-9:

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Formula 1-6]

[Formula 1-7]

[Formula 1-8]

[Formula 1-9]

In Formulas 1-1 to 1-9,

W is O or S;

L ₁ to L ₃ , Ar ₁ , Ar ₂ and R ₁ to R ₈ are as defined in Formulas 1 to 3 above,

R ₆ ′ and R ₇ ′ are as defined for _{R 6} and R ₇ in claim 1, respectively.

Specifically, the compound represented by Formula 1 may be any one selected from the group consisting of:

Meanwhile, the compound represented by Formula 1 may be prepared by, for example, a preparation method as shown in Scheme 1 below.

[Scheme 1]

In Scheme 1, _{descriptions of L 1} to L ₃ , Ar ₁ , Ar ₂ and A are as defined in Formula 1 above, and X is halogen, preferably bromo or chloro. The reaction is a Suzuki coupling reaction, and is preferably performed 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 Preparation Examples to be described later.

Meanwhile, the metal complex compound refers to a complex of a metal selected from the group consisting of alkali metals, alkaline earth metals, transition metals and Group 13 metals in the periodic table.

Specifically, the metal complex compound may be represented by the following Chemical Formula 5, wherein M is a central metal, L ₁₁ is a primary ligand, and L ₁₂ is an auxiliary ligand.

[Formula 5]

M(L ₁₁ ) _n11 (L ₁₂ ) _n12

In Formula 5,

M is lithium, beryllium, manganese, copper, zinc, aluminum, or gallium;

L ₁₁ is substituted or unsubstituted 8-hydroxyquinolinato; Or a substituted or unsubstituted 10-hydroxybenzo [h] quinolinato,

L ₁₂ is halogen; substituted or unsubstituted phenolato; Or a substituted or unsubstituted naphtolato,

n11 is 1, 2, or 3;

n12 is 0 or 1,

n11+n12 is 1, 2, or 3,

When n11 is 2 or more, two or more L ₁₁ are the same as or different from each other.

More specifically, L ₁₁ is 8-hydroxyquinolinato unsubstituted or substituted with halogen or C _{1-4 alkyl;} Or halogen, or C _1-4 alkyl unsubstituted or substituted 10-hydroxybenzo [h] quinolinato,

L ₁₂ is halogen; phenolato unsubstituted or substituted with C _{1-4 alkyl;} It may be naphtolato unsubstituted or substituted with _{C 1-4 alkyl.}

Or, L ₁₁ is 8-hydroxyquinolinato, 2-methyl-8-hydroxyquinolinato, or 10-hydroxybenzo [h] quinolinato,

L ₁₂ may be chloro, o-crezolato, or 2-naphtolato.

For example, the metal complex compound may be 8-hydroxyquinolinato lithium, bis(8-hydroxyquinolinato)zinc, bis(8-hydroxyquinolinato)copper, or bis(8-hydroxyquinolinato)zinc. Earth) Manganese, tris(8-hydroxyquinolinato)aluminum, tris(2-methyl-8-hydroxyquinolinato)aluminum, tris(8-hydroxyquinolinato)gallium, bis(10-hydroxyl Benzo[h]quinolinato)beryllium, bis(10-hydroxybenzo[h]quinolinato)zinc, bis(2-methyl-8-quinolinato)chlorogallium, bis(2-methyl-8-qui Nolinato)(o-crezolato)gallium, bis(2-methyl-8-quinolinato)(1-naphtolato)aluminum and bis(2-methyl-8-quinolinato)(2-naphtolato)gallium is selected from the group consisting of

Such a metal complex compound may be prepared by a conventionally known conventional method.

In addition, the electron transport layer preferably includes the compound represented by Formula 1 and the metal complex compound in a weight ratio of 3:7 to 7:3. In this case, if the ratio is less than 3:7, the lifetime may decrease, and if it exceeds 7:3, the driving voltage may be increased. Specifically, for example, the electron transport layer may include the compound represented by Formula 1 and the metal complex compound in a weight ratio of 3:7, 4:6, 5:5, 6:4, or 7:3. .

electron injection layer

The electron injection layer is a layer that injects electrons from the electrode, has the ability to transport electrons, has an electron injection effect from the cathode, has an excellent electron injection effect with respect to the light emitting layer or the light emitting material, and has excellent thin film forming 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, Perylenetetracarboxylic acid, preorenylidene methane, anthrone and the like, derivatives thereof, metal complex compounds, 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 including a substrate 1 , an anode 2 , a light emitting layer 3 , an electron transport layer 4 , and a cathode 5 . In such a structure, the compound represented by Formula 1 and the metal complex compound are included in the electron transport layer.

2 shows a substrate 1, an anode 2, a hole injection layer 6, a hole transport layer 7, a light emitting layer 3, an electron transport layer 4, an electron injection layer 8 and a cathode 5. An example of an organic light emitting device is shown. In such a structure, the compound represented by Formula 1 and the metal complex compound are 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 the electron injection and transport layer.

The power efficiency (lm/W) of the organic light emitting diode according to the present invention can be expressed as the amount of emitted light with respect to the applied power (P, W). V) and the y-axis is current density (mA/cm ² ) It can be measured through a JV curve indicating the amount of current according to voltage.

The power efficiency value at a voltage of 5 V measured from the JV curve of the organic light emitting device is the JV curve of the organic light emitting device in which the compound represented by Formula 1 and the metal complex compound are included in the electron transport layer in a weight ratio of 5 to 5 It may have a value within ±30% of the power efficiency value at a voltage of 5 V measured from This can be realized when the organic light emitting device includes the compound represented by Formula 1 and the metal complex compound in a weight ratio of 3:7 to 7:3 in the electron transport layer.

In addition, a current efficiency (Cd/A) value of the organic light emitting device may be obtained through a graph representing efficiency according to ^{current density (mA/cm 2 ) when a current is applied to the organic light emitting device.} At this time, ^{the current efficiency (cd/A) of the organic light-emitting device measured at a current density of 10 mA/cm 2} is, under the same measurement conditions, the compound represented by Formula 1 and the metal complex compound in a weight ratio of 5 to 5 Compared to the current efficiency (cd/A) of the organic light emitting device included in the electron transport layer, it may have a value within ±30%, preferably within ±20%, and more preferably within ±15%. Specifically, when the current efficiency (cd/A) value of the organic light emitting device in which the compound represented by Formula 1 and the metal complex compound are included in the electron transport layer in a weight ratio of 5 to 5 is referred to as 'reference current efficiency', the organic The current efficiency change rate (%) of the light emitting device can be calculated as in Equation 1 below.

[Equation 1]

That is, the current efficiency change rate (%) of the organic light emitting device is the current efficiency (cd/A) value of the organic light emitting device and the compound represented by Formula 1 and the metal complex compound are the electron transport layer in a weight ratio of 5 to 5 The absolute value of the difference in the current efficiency (cd/A) value of the organic light emitting device included in As a value divided by the efficiency (cd/A) value, it may have a value within 30%, preferably within 20%, and more preferably within 15%.

This can be realized when the organic light emitting device includes the compound represented by Formula 1 and the metal complex compound in a weight ratio of 3:7 to 7:3 in the electron transport layer.

As such, even if the mixing ratio of the compound represented by Formula 1 and the metal complex compound is different, the range of change in power efficiency and/or current efficiency of the organic light emitting device is not large. Even in manufacturing, it means that the defective rate that can be caused by the LiQ mixing ratio error can be significantly reduced.

^{In addition, the driving voltage measured at a current density of 0.05 mA/cm 2} to 20 mA/cm ² of the organic light-emitting device is 5 V or less, specifically, 3 V to 5 V, more specifically, 3 V to 4 V . Accordingly, the organic light emitting device includes an organic light emitting device including each of the compound represented by Formula 1 and the metal complex compound in an electron transport layer, and a compound having a mother nucleus structure of Formula 1 without including a cyano group and the metal It can be driven at a lower voltage than an organic light-emitting device including a complex compound at the same time.

The organic light emitting device according to the present invention may be manufactured by sequentially stacking the above-described components. At this time, by using a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation, a metal or conductive metal oxide or an alloy thereof is deposited on a substrate to form an anode. And, after forming each of the above-mentioned 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 for the host and the dopant. Here, the solution coating method refers to spin coating, dip coating, doctor blading, inkjet printing, screen printing, spraying, roll coating, and the like, but is not limited thereto.

In addition to this 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.

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

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

manufacturing example 1: Preparation of compound 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). 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 , stirred and refluxed for 5 hours. After cooling to room temperature, the resulting solid was recrystallized from chloroform and ethanol by filtration to prepare Compound 1 (13.4 g, yield 82%).

MS:[M+H] ⁺ = 651

manufacturing example 2: Preparation of compound 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). After adding 2M K ₂ CO ₃ (100 mL), Pd(dba) ₂ (0.5 g), and PCy ₃ (0.5 g), the mixture was stirred and refluxed for 5 hours. After cooling to room temperature, the resulting solid was recrystallized from chloroform and ethanol by filtration to prepare Compound 2 (10.5 g, yield 71%).

MS:[M+H] ⁺ = 701

manufacturing example 3: Preparation of compound 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). After adding 2M K ₂ CO ₃ (100 mL), Pd(dba) ₂ (0.6 g), and PCy ₃ (0.6 g), the mixture was stirred and refluxed for 5 hours. After cooling to room temperature, the resulting solid was recrystallized from chloroform and ethanol by filtration to prepare Compound 3 (12.6 g, yield 78%).

MS:[M+H] ⁺ = 665

manufacturing example 4: Preparation of compound 4

The compound A4 (10 g, 22.9 mmol) and the compound B2 (10 g, 22.9 mmol) were added to tetrahydrofuran (150 mL). After adding 2M K ₂ CO ₃ (100 mL), Pd(dba) ₂ (0.6 g), and PCy ₃ (0.6 g), the mixture was stirred and refluxed for 5 hours. After cooling to room temperature, the resulting solid was recrystallized from chloroform and ethanol by filtration to prepare Compound 4 (10.4 g, yield 68%).

MS:[M+H] ⁺ = 665

manufacturing example 5: Preparation of compound 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). After adding 2M K ₂ CO ₃ (100 mL), Pd(dba) ₂ (0.5 g), and PCy ₃ (0.5 g), the mixture was stirred and refluxed for 5 hours. After cooling to room temperature, the resulting solid was recrystallized from chloroform and ethanol by filtration to prepare Compound 5 (9.9 g, yield 62%).

MS:[M+H] ⁺ = 890

manufacturing example 6: Preparation of compound 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). After adding 2M K ₂ CO ₃ (100 mL), Pd(dba) ₂ (0.6 g), and PCy ₃ (0.6 g), the mixture was stirred and refluxed for 5 hours. After cooling to room temperature, the resulting solid was recrystallized from chloroform and ethanol by filtration to prepare Compound 6 (12.9 g, yield 80%).

MS:[M+H] ⁺ = 665

manufacturing example 7: Preparation of compound 7

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

MS:[M+H] ⁺ = 651

manufacturing example 8: Preparation of compound 8

Compound 8 was prepared in the same manner as in Preparation Example 1, except that Compound B7 was used instead of Compound B1 in Preparation Example 1.

MS:[M+H] ⁺ = 727

manufacturing example 9: Preparation of compound 9

Compound 9 was prepared in the same manner as in Preparation Example 1, except that Compound A7 was used instead of Compound A1 in Preparation Example 1, and Compound B8 was used instead of Compound B1.

MS:[M+H] ⁺ = 777

manufacturing example 10: Preparation of compound 10

Compound 10 was prepared in the same manner as in Preparation Example 1, except that Compound A4 was used instead of Compound A1 in Preparation Example 1, and Compound B9 was used instead of Compound B1.

MS:[M+H] ⁺ = 589

manufacturing example 11: Preparation of compound 11

Compound 11 was prepared in the same manner as in Preparation Example 1, except that Compound A3 was used instead of Compound A1 in Preparation Example 1, and Compound B10 was used instead of Compound B1.

MS:[M+H] ⁺ = 741

manufacturing example 12: Preparation of compound 12

Compound 12 was prepared in the same manner as in Preparation Example 1, except that Compound A3 was used instead of Compound A1 in Preparation Example 1, and Compound B11 was used instead of Compound B1.

MS:[M+H] ⁺ = 893

manufacturing example 13: Preparation of compound 13

Compound 13 was prepared in the same manner as in Preparation Example 1, except that Compound A5 was used instead of Compound A1 in Preparation Example 1, and Compound B9 was used instead of Compound B1.

MS:[M+H] ⁺ = 737

manufacturing example 14: Preparation of compound 14

Compound 14 was prepared in the same manner as in Preparation Example 1, except that Compound A8 was used instead of Compound A1 in Preparation Example 1, and Compound B12 was used instead of Compound B1.

MS:[M+H] ⁺ = 751

manufacturing example 15: Preparation of compound 15

Compound 15 was prepared in the same manner as in Preparation Example 1, except that Compound A3 was used instead of Compound A1 in Preparation Example 1, and Compound B13 was used instead of Compound B1.

MS:[M+H] ⁺ = 665

manufacturing example 16: Preparation of compound 16

Compound 16 was prepared in the same manner as in Preparation Example 1, except that Compound A3 was used instead of Compound A1 in Preparation Example 1, and Compound B14 was used instead of Compound B1.

MS:[M+H] ⁺ = 664

manufacturing example 17: Preparation of compound 17

Compound 17 was prepared in the same manner as in Preparation Example 1, except that Compound A3 was used instead of Compound A1 in Preparation Example 1, and Compound B12 was used instead of Compound B1.

MS:[M+H] ⁺ = 665

Example 1-1

A glass substrate (corning 7059 glass) coated with a thin film of ITO (indium tin oxide) to a thickness of 1000 Å was placed in distilled water in which a dispersant was dissolved and washed with ultrasonic waves. The detergent used was a product of Fischer Co., and the distilled water was manufactured by Millipore Co. Secondary filtered distilled water was used as a filter of the product. After washing 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 thus 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.

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

Compound 1 and LiQ (Lithium Quinolate) prepared in Preparation Example 1 were vacuum-deposited in a weight ratio of 50:50 on the light emitting layer to form an electron transport layer to a thickness of 350 Å.

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 material was maintained at 0.4 to 0.7 Å/sec, the deposition rate of lithium fluoride of the negative electrode was maintained at 0.3 Å/sec, and the deposition rate of aluminum was maintained at 2 Å/sec, and the vacuum degree during deposition was 2 × 10 ^-7 To maintain ~ 5 × 10 ^-6 torr, an organic light emitting device was manufactured.

The compound used in Example 1 is as follows.

Example 1-2 to Example 1-17 and comparative example 1-1 to 1-8

An organic light emitting diode was manufactured in the same manner as in Example 1-1, except that the compounds shown in Table 1 below were used instead of Compound 1 as the electron transport layer material in Example 1-1.

The compounds used in the above Examples are summarized as follows.

The compounds used in the comparative examples are summarized as follows.

Experimental example One

For the organic light emitting devices prepared in Examples 1-1 to 1-17 and Comparative Examples 1-1 to 1-8, the driving voltage and current efficiency at a current density of ^{10 mA/cm 2 , and 20 mA/cm At} a current density of 2, the time (LT98) to be 98% of the initial luminance was measured, and the results are shown in Table 1 below.

compound
(electron transport layer) drive voltage
(V
@10mA/cm ² ) current efficiency
(cd/A
@10mA/cm ² ) LT98
(hr
@20mA/cm ² ) Example 1-1 compound 1 3.75 5.29 60 Example 1-2 compound 2 3.65 5.33 60 Examples 1-3 compound 3 3.92 5.45 62 Examples 1-4 compound 4 3.60 5.42 61 Examples 1-5 compound 5 3.80 5.30 45 Examples 1-6 compound 6 3.88 5.45 62 Examples 1-7 compound 7 3.78 5.30 56 Examples 1-8 compound 8 3.71 5.31 49 Examples 1-9 compound 9 3.80 5.28 41 Examples 1-10 compound 10 3.75 5.33 58 Examples 1-11 compound 11 3.72 5.38 42 Examples 1-12 compound 12 3.72 5.42 42 Examples 1-13 compound 13 3.73 5.50 60 Examples 1-14 compound 14 3.78 5.21 48 Examples 1-15 compound 15 3.79 5.34 50 Examples 1-16 compound 16 3.77 5.45 55 Examples 1-17 compound 17 3.65 5.20 49 Comparative Example 1-1 ET1 4.15 5.00 30 Comparative Example 1-2 ET2 4.11 4.93 36 Comparative Example 1-3 ET3 4.22 4.94 32 Comparative Example 1-4 ET4 4.15 4.69 25 Comparative Example 1-5 ET5 5.20 4.27 7 Comparative Example 1-6 ET6 4.55 4.59 38 Comparative Example 1-7 ET7 4.20 4.91 32 Comparative Examples 1-8 ET8 4.50 5.00 20

As shown in Table 1, the organic light emitting device using the compound represented by Formula 1 as a material for the electron transport layer, compared to the organic light emitting device of Comparative Example, shows excellent characteristics in terms of driving voltage, luminous efficiency and lifespan. can be checked Considering that the luminous efficiency and lifespan characteristics of the organic light emitting device generally have a trade-off relationship with each other, the organic light emitting device employing the compound of the present invention has significantly improved device characteristics compared to the comparative example device. It can be seen that indicates

Example 2-1

Example 1-1, except that compound 1 prepared in Preparation Example 1 and LiQ (Lithium Quinolate) were vacuum-deposited in a weight ratio of 70:30 to form an electron transport layer to a thickness of 350 Å in Example 1-1. An organic light emitting device was manufactured using the same method as described above.

Example 2-2 to Example 2-17 and comparative example 2-1 to 2-8

An organic light emitting diode was manufactured in the same manner as in Example 2-1, except that the compounds shown in Table 2 below were used instead of Compound 1 as the electron transport layer material in Example 2-1.

Experimental example 2

For the organic light emitting devices prepared in Examples 2-1 to 2-17 and Comparative Examples 2-1 to 2-8, the current efficiency at a current density of ^{10 mA/cm 2 was measured for the organic light emitting device.} Thus, the results are shown in Table 2 below.

In addition, for each Example and Comparative Example, as in Formula 1, the same compound was used, but the mixing ratio with LiQ was 50:50, 'absolute value of difference in current efficiency' with the Example and Comparative Example of Experimental Example 1 , obtained by dividing the absolute value of the difference by the current efficiency value of Experimental Example 1 in which the mixing ratio with LiQ is 50:50 (%), and the values are shown in Table 2 below. For example, in the case of Example 2-1, the absolute value of the difference in current efficiency with that of Example 1-1 was obtained, and a value obtained by dividing the obtained absolute value by the current efficiency of Example 1-1 was calculated as an efficiency change rate value.

In addition, the current efficiency (Cd/A) with ^{respect to the current density (mA/cm 2} ) was measured for each of the organic light-emitting device prepared in Examples 1-15 and the organic light-emitting device prepared in Examples 2-15, and FIG. 3 As shown in, the current efficiency (Cd/A) with ^{respect to the current density (mA/cm 2} ) was measured for each of the organic light-emitting device prepared in Comparative Example 1-4 and the organic light-emitting device prepared in Comparative Example 2-4. 4 is shown.

compound
(electron transport layer) current efficiency
(cd/A
@10mA/cm ² ) using the same compound
Experimental Example 1
Current efficiency difference
(cd/A) Current efficiency change rate
(%) Example 2-1 compound 1 4.90 0.39 7.4 Example 2-2 compound 2 5.20 0.13 2.4 Example 2-3 compound 3 4.87 0.58 10.6 Example 2-4 compound 4 4.95 0.47 8.7 Example 2-5 compound 5 4.92 0.38 7.2 Example 2-6 compound 6 4.89 0.56 10.3 Example 2-7 compound 7 5.22 0.08 1.5 Examples 2-8 compound 8 5.28 0.03 0.6 Examples 2-9 compound 9 5.18 0.10 1.9 Example 2-10 compound 10 5.2 0.13 2.4 Example 2-11 compound 11 5.3 0.08 1.5 Example 2-12 compound 12 5.2 0.22 4.1 Examples 2-13 compound 13 5.31 0.19 3.5 Examples 2-14 compound 14 5.1 0.11 2.1 Examples 2-15 compound 15 4.8 0.54 10.1 Examples 2-16 compound 16 5.3 0.15 2.8 Example 2-17 compound 17 5.21 0.01 0.2 Comparative Example 2-1 ET1 3.40 1.60 32.00 Comparative Example 2-2 ET2 3.41 1.52 30.83 Comparative Example 2-3 ET3 3.34 1.60 32.39 Comparative Example 2-4 ET4 3.18 1.51 32.20 Comparative Example 2-5 ET5 2.94 1.33 31.15 Comparative Example 2-6 ET6 3.07 1.52 33.12 Comparative Example 2-7 ET7 3.38 1.53 31.16 Comparative Example 2-8 ET8 3.40 1.60 32.00

As can be seen in Table 2, FIGS. 3 and 4, the organic light emitting device using the compound represented by Formula 1 as a material for the electron transport layer, compared to the organic light emitting device using the compound of Comparative Example, has a LiQ mixing ratio It can be seen that the change in current efficiency according to the change is remarkably small. Accordingly, when the compound represented by Formula 1 is employed as a material for the electron transport layer of the organic light emitting device, even if the organic light emitting device is mass-produced for commercial production, the defect rate that may be caused by the LiQ mixing ratio error is significantly reduced. can be

1: Substrate 2: Anode
3: light emitting layer 4: electron transport layer
5: Cathode 6: Hole injection layer
7: hole transport layer 8: electron injection layer

Claims (14)

anode,
cathode,
a light emitting layer between the anode and the cathode; and
An electron transport layer between the cathode and the light emitting layer,
The electron transport layer comprises a compound represented by the following formula (1) and a metal complex compound,
Organic light emitting device:
[Formula 1]

In Formula 1,
L ₁ to L ₃ are each independently, a single bond; _{or C 6-20} arylene unsubstituted or substituted with cyano;
Ar ₁ and Ar _{2 are each independently C 6-20} aryl unsubstituted or substituted with methyl or cyano;
A is represented by the following formula 2 or 3,
[Formula 2]

[Formula 3]

In Formulas 2 and 3,
W is O, S, CR ₉ R ₁₀ , or SiR ₁₁ R ₁₂ ,
T is a benzene, naphthalene, or phenanthrene ring fused with a neighboring pentacyclic ring,
R ₁ to R ₈ are each independently hydrogen; heavy hydrogen; or cyano, or adjacent R ₆ and R ₇ may combine with each other to form a spiro ring structure,
R ₉ to R ₁₂ are each independently hydrogen; heavy hydrogen; cyano; 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,
a1 is an integer from 0 to 3,
a2 to a6 and a8 are each independently an integer of 0 to 4,
a7 is an integer from 0 to 5;
When a1 to a8 are each 2 or more, the structures in the two or more parentheses are the same as or different from each other,
* represents a position connected to _{L 3} of Formula 1,
However, _{at least one of L 1} to L ₃ , Ar ₁ , Ar ₂ and A is substituted with cyano.
According to claim 1,
The compound represented by Formula 1 is represented by the following Formula 1A, 1B, or 1C,
Organic light emitting device:
[Formula 1A]

In Formula 1A,
L _{1 To} L ₃ , Ar ₁ And Ar _{2 Are} as defined in claim 1,
W is O or S;
R ₁ to R ₄ are each independently hydrogen; heavy hydrogen; or cyano;
provided that at least one of _{L 1} to L _{3 is C 6-20} arylene substituted with cyano;
at least one of Ar ₁ and Ar _{2 is C 6-20} aryl substituted with cyano; or
At least one of R ₁ to R _{4 is cyano,}
[Formula 1B]

In Formula 1B,
L ₁ to L ₃ , Ar ₁ and Ar ₂ are as defined in claim 1,
T is a benzene, naphthalene, or phenanthrene ring fused with a neighboring pentacyclic ring,
R ₅ to R ₈ are each independently hydrogen; heavy hydrogen; or cyano;
provided that at least one of _{L 1} to L _{3 is C 6-20} arylene substituted with cyano;
at least one of Ar ₁ and Ar _{2 is C 6-20} aryl substituted with cyano; or
At least one of R ₁ to R _{4 is cyano,}
[Formula 1C]

In Formula 1C,
L ₁ to L ₃ , Ar ₁ and Ar ₂ are as defined in claim 1,
R ₅ to R ₈ , R ₆ ′ and R ₇ ′ are each independently hydrogen; heavy hydrogen; or cyano;
provided that at least one of _{L 1} to L _{3 is C 6-20} arylene substituted with cyano;
at least one of Ar ₁ and Ar _{2 is C 6-20} aryl substituted with cyano; or
At least one of R ₅ to R ₈ , R ₆ ′ and R _{7 ′ is cyano.}
According to claim 1,
L ₁ to L ₃ are each independently, a single bond; phenylene unsubstituted or substituted with cyano; unsubstituted or cyano-substituted biphenylrylene; or terphenylrylene unsubstituted or substituted with cyano;
organic light emitting device.
According to claim 1,
Ar ₁ and Ar ₂ are each independently selected from phenyl unsubstituted or substituted with cyano; biphenylyl unsubstituted or substituted with cyano; terphenylyl unsubstituted or substituted with cyano; or 9,9-dimethylfluorene unsubstituted or substituted with cyano;
organic light emitting device.
According to claim 1,
A is any one selected from the group consisting of the following formulas 4a to 4e,
Organic light emitting device:

In Formulas 4a to 4e,
W is O or S;
R ₁ to R ₈ are as defined in claim 1,
R ₆ ' and R ₇ ' are as defined for _{R 6} and R ₇ in claim 1, respectively,
* represents a position connected to _{L 3 in} Formula 1 above.
6. The method of claim 5,
R ₁ to R ₈ , R ₆ ' and R ₇ ' are each independently hydrogen or cyano;
organic light emitting device.
6. The method of claim 5,
In Formula 4a,
R ₁ to R ₄ are hydrogen; or one of R ₁ to R ₄ is cyano, the other is hydrogen,
In Formulas 4b to 4d,
R ₅ to R ₈ are hydrogen; or one of R ₅ to R ₈ is cyano, the other is hydrogen,
In Formula 4e,
R ₅ to R ₈ , R ₆ ′ and R ₇ ′ are hydrogen; or one of R ₅ to R ₈ , R ₆ ' and R ₇ ' is cyano and the other is hydrogen;
organic light emitting device.
According to claim 1,
The compound represented by Formula 1 is any one selected from the group consisting of the following Formulas 1-1 to 1-9,
Organic light emitting device:
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Formula 1-6]

[Formula 1-7]

[Formula 1-8]

[Formula 1-9]

In Formulas 1-1 to 1-9,
W is O or S;
L ₁ to L ₃ , Ar ₁ , Ar ₂ and R ₁ to R ₈ are as defined in claim 1,
R ₆ ′ and R ₇ ′ are as defined for _{R 6} and R ₇ in claim 1, respectively.
According to claim 1,
The compound represented by Formula 1 is any one selected from the group consisting of
Organic light emitting device:

According to claim 1,
The metal complex compound is represented by the following formula (5),
Organic light emitting device:
[Formula 5]
M(L ₁₁ ) _n11 (L ₁₂ ) _n12
In Formula 5,
M is lithium, beryllium, manganese, copper, zinc, aluminum, or gallium;
L ₁₁ is substituted or unsubstituted 8-hydroxyquinolinato; Or a substituted or unsubstituted 10-hydroxybenzo [h] quinolinato,
L ₁₂ is halogen; substituted or unsubstituted phenolato; Or a substituted or unsubstituted naphtolato,
n11 is 1, 2, or 3;
n12 is 0 or 1,
n11+n12 is 1, 2, or 3.
According to claim 1,
The metal complex compound is 8-hydroxyquinolinato lithium, bis(8-hydroxyquinolinato)zinc, bis(8-hydroxyquinolinato)copper, bis(8-hydroxyquinolinato)manganese, Tris(8-hydroxyquinolinato)aluminum, tris(2-methyl-8-hydroxyquinolinato)aluminum, tris(8-hydroxyquinolinato)gallium, bis(10-hydroxybenzo[h] Quinolinato) beryllium, bis (10-hydroxybenzo [h] quinolinato) zinc, bis (2-methyl-8-quinolinato) chlorogallium, bis (2-methyl-8-quinolinato) ( group consisting of o-crezolato)gallium, bis(2-methyl-8-quinolinato)(1-naphtolato)aluminum and bis(2-methyl-8-quinolinato)(2-naphtolato)gallium Any one selected from
organic light emitting device.
According to claim 1,
The electron transport layer comprises the compound represented by Formula 1 and the metal complex compound in a weight ratio of 3:7 to 7:3,
organic light emitting device.
According to claim 1,
The current efficiency (cd/A) of the organic light emitting device measured at a current density of 10 mA/cm ² is the compound represented by Formula 1 and the metal complex compound in a weight ratio of 5 to 5 under the same measurement conditions. Compared to the current efficiency (cd/A) of the organic light emitting device included in the transport layer, having a value within ±30%,
organic light emitting device.
According to claim 1,
The driving voltage measured at a current density ^{of 0.05 mA/cm 2} to 20 mA/cm ² of the organic light-emitting device is 3 V to 5 V,
organic light emitting device.

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