KR20210079187A - Organic light emitting device - Google Patents

Abstract

Provided is an organic light emitting element which increases a driving voltage, efficiency and a lifespan. The organic light emitting element includes an anode, a cathode, and a light emitting layer between the anode and the cathode.

Description

Organic light emitting device

The present invention relates to an organic light emitting device having improved driving voltage, efficiency, and 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 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, and 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 such an 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 these excitons are When it falls back to the ground state, it lights up.

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

Korean Patent Publication No. 10-2000-0051826

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

The present invention provides the following organic light emitting device:

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

The light emitting layer comprises a first compound represented by the following formula (1) and a second compound represented by the following formula (2),

Organic light emitting device:

[Formula 1]

In Formula 1,

A is a benzene ring fused with two adjacent pentagonal rings,

Ar ₁ to Ar ₃ are each independently substituted or unsubstituted C _6-60 aryl; _{Or a substituted or unsubstituted C 5-60} heteroaryl containing any one or more heteroatoms selected from the group consisting of N, O and S;

R ₁ is each independently hydrogen; heavy hydrogen; halogen; cyano; substituted or unsubstituted C _1-60 alkyl; substituted or unsubstituted C _1-60 alkoxy; substituted or unsubstituted C _2-60 alkenyl; substituted or unsubstituted C _2-60 alkynyl; substituted or unsubstituted C _3-60 cycloalkyl; substituted or unsubstituted C _6-60 aryl; _{Or substituted or unsubstituted C 2-60} heteroaryl containing any one or more heteroatoms selected from the group consisting of N, O and S,

x is an integer from 1 to 10,

provided _{that at least one of Ar 1} to Ar ₃ , and R ₁ is substituted with one or more deuterium, or _{at least one of R 1} is deuterium, wherein the first compound is substituted with at least 5 deuterium,

[Formula 2]

In Formula 2,

B is a benzene ring fused with two adjacent pentagonal rings, respectively,

Ar ₄ is a substituted or unsubstituted C _6-60 aryl,

Ar ₅ is substituted or unsubstituted C _6-60 aryl; _{Or a substituted or unsubstituted C 5-60} heteroaryl containing one heteroatom selected from the group consisting of N, O and S,

R ₂ are each independently hydrogen; heavy hydrogen; halogen; cyano; substituted or unsubstituted C _1-60 alkyl; substituted or unsubstituted C _1-60 alkoxy; substituted or unsubstituted C _2-60 alkenyl; substituted or unsubstituted C _2-60 alkynyl; substituted or unsubstituted C _3-60 cycloalkyl; substituted or unsubstituted C _6-60 aryl; _{Or substituted or unsubstituted C 2-60} heteroaryl containing any one or more heteroatoms selected from the group consisting of N, O and S,

y is an integer from 1 to 10;

The above-described organic light emitting device includes the first compound represented by Formula 1 and the second compound represented by Formula 2 in the light emitting layer, and thus has excellent driving voltage, efficiency, and lifetime.

FIG. 1 shows an example of an organic light emitting device including a substrate 1 , an anode 2 , a light emitting layer 3 , and a cathode 4 .
2 is a substrate (1), an anode (2), a hole injection layer (5), a hole transport layer (6), an electron blocking layer (7), a light emitting layer (3), a hole blocking layer (8), an electron injection and transport layer ( 9) and an example of an organic light-emitting device including a cathode 4 are shown.

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

또는

는 다른 치환기에 연결되는 결합을 의미한다. In this specification,

or

means a bond connected to another substituent.

As used herein, the term "substituted or unsubstituted" refers to deuterium; halogen group; nitrile 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 atom means that it is substituted or unsubstituted with one or more substituents selected from the group consisting of a heterocyclic group containing one or more atoms, or substituted or unsubstituted with two or more substituents connected among 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, the heterocyclic group is a heterocyclic group including 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 the heterocyclic group 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, 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, thiadia and a jolyl group, a phenothiazinyl group, and a 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 of the above-described heterocyclic group 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 the above-described heterocyclic group 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 heterocyclic group is not a monovalent group, and the description of the above-described heterocyclic group may be applied, except that it is formed by combining two substituents.

The organic light emitting device according to the present invention has a structure in which an anode, a light emitting layer and a cathode are sequentially stacked on a substrate (normal type), or an organic light emitting device having an inverted tyoe structure in which a cathode, a light emitting layer, and an anode are sequentially stacked on a substrate It may be a light emitting device. In addition, the organic light emitting device, between the anode and the light emitting layer, may optionally further include one or more layers of a hole injection layer, a hole transport layer, and an electron suppression layer, and between the cathode and the light emitting layer, a hole blocking layer, an electron At least one of an injection layer and an electron transport layer may be further included. In addition, the electron injection layer and the electron transport layer may be included in the form of a single layer of the electron injection and transport layer, rather than a separate layer.

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

positive and negative

The anode and cathode used in the present invention mean electrodes used in an organic light emitting device.

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.

hole injection layer

The organic light emitting diode according to the present invention may further include a hole injection layer on the anode, if necessary.

The hole injection layer is a layer for injecting holes from the electrode, and as a hole injection material, it has the ability to transport holes, so it has a hole injection effect at the anode, an excellent hole injection effect with respect to the light emitting layer or the light emitting material, and is produced in the light emitting layer A compound which prevents the movement of excitons to the electron injection layer or the electron injection material and is excellent in the ability to form a thin film is preferable. In addition, it is preferable that 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-based organic material. of organic substances, anthraquinones, polyaniline and polythiophene-based conductive polymers, and the like, but are not limited thereto.

hole transport layer

The organic light emitting diode according to the present invention may include a hole transport layer on the anode (or on the hole injection layer if there is a hole injection layer) if necessary.

The hole transport layer is a layer that receives holes from the anode or hole injection layer and transports them to the light emitting layer. As a hole transport material, the hole transport material is a material capable of transporting holes from the anode or hole injection layer to the light emitting layer. Larger materials are suitable.

Specific examples of the hole transport material 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 layer used in the present invention refers to a layer capable of emitting light in the visible ray region by combining holes and electrons transferred from the anode and the cathode. In general, the emission layer includes a host material and a dopant material, and in the present invention, the first compound represented by Formula 1 and the second compound represented by Formula 2 are included as hosts.

Preferably, the first compound represented by Formula 1 may be substituted with 5 or more deuterium. Specifically, in Formula 1, Ar ₁ to Ar ₃ , and _{at least one of R 1} is substituted with one or more deuterium, or _{at least one of R 1} is deuterium, whereby the first compound is 5 or more in the compound. , or 6 or more, or 7 or more, or 8 or more, or 10 or more deuterium, or the first compound may be completely substituted with deuterium.

Preferably, Chemical Formula 1 may be represented by any one selected from the group consisting of the following Chemical Formulas 1-1 to 1-6:

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Formula 1-6]

In Formulas 1-1 to 1-6, Ar ₁ to Ar ₃ , R ₁ , and x are as defined above.

In Formula 1, preferably, Ar _{1 To} Ar ₃ are each independently phenyl, biphenyl, terphenyl, dibenzofuranyl, dibenzothiophenyl, fluorenyl, 9,9-dimethylfluorenyl, 9 ,9-diphenylfluorenyl, carbazol-9-yl, or 9-phenyl-9H-carbazolyl.

In Formula 1, more preferably _{, at least one of Ar 1} to Ar ₃ is phenyl, and the rest are each independently phenyl, biphenyl, terphenyl, dibenzofuranyl, dibenzothiophenyl, fluorenyl, 9 ,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, carbazol-9-yl, or 9-phenyl-9H-carbazolyl.

In addition, _{at least one of Ar 1} to Ar ₃ may be substituted with one or more deuterium. For example, _{at least one of Ar 1} to Ar ₃ may be selected from the group consisting of the following structures:

In the above formula, a is an integer from 1 to 5,

b is an integer from 0 to 4, c is an integer from 0 to 5, but b and c are not 0 at the same time,

d is each independently an integer from 0 to 3, e is an integer from 0 to 5, but d and e are not 0 at the same time,

f is an integer from 0 to 3, g is each independently an integer from 0 to 5, but f and g are not 0 at the same time,

h is an integer from 0 to 3, i is an integer from 0 to 4, provided that h and i are not 0 at the same time,

j is an integer from 0 to 3, k is an integer from 0 to 4, l is each independently an integer from 0 to 5, wherein j, k and l are not 0 at the same time,

m is an integer from 0 to 4, n is an integer from 0 to 4, provided that m and n are not 0 at the same time,

o is an integer from 0 to 3, p is an integer from 0 to 4, and q is an integer from 0 to 5, provided that o, p, and q are not 0 at the same time.

Also preferably _{, at least one of Ar 1} to Ar ₃ may be substituted with 5 or more deuterium.

More preferably, in Formula 1, _{at least one of Ar 1} to Ar ₃ is phenyl substituted with 5 deuterium, and the remainder is unsubstituted phenyl, biphenyl, terphenyl, dibenzofuranyl, and dibenzothi offenyl, fluorenyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, carbazol-9-yl, or 9-phenyl-9H-carbazolyl.

In one example, Ar _{1 To} Ar _{3 Are} all phenyl, wherein Ar _{1 To} Ar ₃ At least one of, specifically, Ar _{1 To} Ar ₃ Any one, or two, or all three are 5 deuterium may be substituted.

In another example, one of Ar ₁ to Ar ₃ is unsubstituted, biphenyl, terphenyl dibenzofuranyl, dibenzothiophenyl, fluorenyl, 9,9-dimethylfluorenyl, 9, 9-diphenylfluorenyl, carbazol-9-yl, or 9-phenyl-9H-carbazolyl, the remainder being phenyl, wherein at least one of the remainders, i.e. one or both of the others, is 5 deuterium can be replaced with

Also preferably _{, at least one of Ar 1} to Ar ₃ is substituted with 5 or more deuterium, biphenyl, terphenyl, dibenzofuranyl, dibenzothiophenyl, fluorenyl, 9,9-dimethyl fluorenyl, 9,9-diphenylfluorenyl, carbazol-9-yl, or 9-phenyl-9H-carbazolyl, and the rest may each independently be unsubstituted phenyl or unsubstituted biphenyl .

For example, one of Ar ₁ to Ar ₃ may be biphenyl substituted with 5 deuterium, and the rest may each independently be unsubstituted phenyl or unsubstituted biphenyl. In this case, the biphenyl substituted with 5 deuterium may be represented by the following structure as an example.

In the above formula, r is an integer of 0 to 4, more specifically 0.

In another example, _{two of Ar 1} to Ar ₃ may be biphenyl substituted with 5 deuterium, and the remainder may be unsubstituted phenyl. In this case, the biphenyl substituted with 5 deuterium may be represented by the above structure.

In another example, _{one of Ar 1} to Ar ₃ is completely substituted with deuterium, biphenyl, terphenyl, dibenzofuranyl, dibenzothiophenyl, fluorenyl, 9,9-dimethylfluorenyl , 9,9-diphenylfluorenyl, carbazol-9-yl, or 9-phenyl-9H-carbazolyl, and all others may be unsubstituted phenyl.

Also preferably, the Ar ₁ to Ar ₃ are each independently phenyl, biphenyl, terphenyl, dibenzofuranyl, dibenzothiophenyl, fluorenyl, 9,9-dimethylfluorenyl, 9,9 -diphenylfluorenyl, carbazol-9-yl, or 9-phenyl-9H-carbazolyl, wherein Ar ₁ to Ar ₃ may be completely substituted with deuterium.

In addition, in Formula 1, preferably, _{all of R 1} may be hydrogen. In this case, in Formula 1, x is an integer of 10, and _{at least one of Ar 1} to Ar ₃ is substituted with 5 or more deuterium.

In addition, in Formula 1, preferably _{, at least 5 of R 1} may be deuterium, and the remainder may be hydrogen. In this case, in Formula 1, x is an integer of 10. For example, in Formula 1, and five of the R _1, or six, or seven, or eight deuterium, and the other may be a may be hydrogen, or R _1, all 10 dogs deuterium.

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

.

.

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

[Scheme 1]

In Scheme 1, Ar ₁ to Ar ₃ , R ₁ , and x are as defined in Formula 1 above, and X is halogen, preferably chloro or bromo.

Scheme 1 is an amine substitution reaction, preferably performed in the presence of a palladium catalyst and a base, and the reactor for the amine substitution reaction can be changed as known in the art. The manufacturing method may be more specific in Preparation Examples to be described later.

Meanwhile, Chemical Formula 2 may be preferably represented by any one selected from the group consisting of the following Chemical Formulas 2-1 to 2-6, and more preferably, Chemical Formula 2 is represented by the following Chemical Formulas 2-1 to 2-3 It may be represented by any one selected from the group consisting of:

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Formula 2-4]

[Formula 2-5]

[Formula 2-6]

In Formulas 2-1 to 2-6, Ar ₄ , Ar ₅ , R ₂ , and y are as defined above.

In Formula 2, preferably Ar ₄ and Ar ₅ may each independently be unsubstituted C _6-30 aryl, more preferably Ar ₄ and Ar ₅ are each independently, unsubstituted, phenyl, biphenyl, terphenyl, fluorenyl, 9,9-dimethylfluorenyl, or 9,9-diphenylfluorenyl.

In addition, in Formula 2, preferably Ar ₄ is unsubstituted C _6-30 aryl, Ar _{5 is unsubstituted C 5-} containing one heteroatom selected from the group consisting of N, O and S ₆₀ may be heteroaryl, more preferably Ar ₄ is unsubstituted, phenyl, biphenyl or terphenyl, Ar ₅ is unsubstituted, dibenzofuranyl, dibenzothiophenyl, carbazole-9- yl, or 9-phenyl-9H-carbazolyl.

Preferably, in Formula 2, R ₂ may be all hydrogen, and in this case, y may be an integer of 10.

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

.

.

The compound represented by Chemical Formula 2 may be prepared by, for example, a preparation method as shown in Scheme 2 below.

[Scheme 2]

In Scheme 2, Ar ₄ , Ar ₅ , R ₂ , and y are as defined in Formula 2 above, and Y is halogen, preferably chloro or bromo. Ar is as defined _{for Ar 4} or Ar _{5 .}

Scheme 2 is an amine substitution reaction, preferably performed in the presence of a palladium catalyst and a base, and the reactor for the amine substitution reaction can be changed as known in the art. The manufacturing method may be more specific in Preparation Examples to be described later.

Although the reaction of compound (III) and compound (IV) in Scheme 2 is shown in one step, when Ar ₄ and Ar ₅ are different from each other in compound (2), Ar in compound (IV) is replaced with Ar ₄ and Ar ₅ It may be performed in two steps by changing to a functional group corresponding to each. At this time, the order of the reaction steps is not particularly limited.

Preferably, the weight ratio of the first compound represented by Formula 1 and the second compound represented by Formula 2 in the light emitting layer is 10:90 to 90:10, more preferably 20:80 to 80:20, 30:70 to 70:30, 30:70 to 50:50, or 30:70 to 40:60.

Meanwhile, the light emitting layer may further include a dopant in addition to the host. The dopant material is not particularly limited as long as it is a material used in an organic light emitting device. Examples include an aromatic amine derivative, a strylamine compound, a boron complex, a fluoranthene compound, and a metal complex. 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 includes, but is not limited to, an iridium complex, a platinum complex, and the like.

electron transport layer

The organic light emitting diode according to the present invention may include an electron transport layer on the light emitting layer, if necessary.

The electron transport layer is a layer that receives electrons from the electron injection layer formed on the cathode or the cathode, transports electrons to the light emitting layer, and suppresses the transfer of holes in the light emitting layer. As an electron transport material, electrons are well injected from the cathode As a material that can receive and transfer to the light emitting layer, a material with high electron mobility is suitable.

Specific examples of the electron transport material include an Al complex of 8-hydroxyquinoline; complexes containing Alq _{3 ;} organic radical compounds; hydroxyflavone-metal complexes, and the like, but are not limited thereto. The electron transport layer may be used with any desired cathode material as used in accordance with the prior art. In particular, examples of suitable cathode materials are conventional materials having a low work function and followed by a layer of aluminum or silver. Specifically cesium, barium, calcium, ytterbium and samarium, followed in each case by an aluminum layer or a silver layer.

electron injection layer

The organic light emitting device according to the present invention may further include an electron injection layer on the light emitting layer (or on the electron transport layer if the electron transport layer is present) if necessary.

The electron injection layer is a layer that injects electrons from the electrode, has the ability to transport electrons, has an electron injection effect from the cathode, an excellent electron injection effect on the light emitting layer or the light emitting material, and hole injection of excitons generated in the light emitting layer. It is preferable to use a compound which prevents movement to a layer and is excellent in the ability to form a thin film.

Specific examples of the material that can be used as the electron injection layer include fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preole nylidene methane, anthrone, and the like, derivatives thereof, metal complex compounds, nitrogen-containing 5-membered ring derivatives, and the like, but are not limited thereto.

Examples of the metal complex compound include 8-hydroxyquinolinato lithium, bis(8-hydroxyquinolinato)zinc, bis(8-hydroxyquinolinato)copper, bis(8-hydroxyquinolinato)manganese, Tris(8-hydroxyquinolinato)aluminum, tris(2-methyl-8-hydroxyquinolinato)aluminum, tris(8-hydroxyquinolinato)gallium, bis(10-hydroxybenzo[h] Quinolinato) beryllium, bis (10-hydroxybenzo [h] quinolinato) zinc, bis (2-methyl-8-quinolinato) chlorogallium, bis (2-methyl-8-quinolinato) ( o-crezolato)gallium, bis(2-methyl-8-quinolinato)(1-naphtolato)aluminum, bis(2-methyl-8-quinolinato)(2-naphtolato)gallium, etc. However, the present invention is not limited thereto.

organic light emitting device

The structure of the organic light emitting device according to the present invention is illustrated in FIGS. 1 and 2 . FIG. 1 shows an example of an organic light emitting device including a substrate 1 , an anode 2 , a light emitting layer 3 , and a cathode 4 . Figure 2 shows a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, an electron blocking layer 7, a light emitting layer 3, a hole blocking layer 8, an electron injection and transport layer An example of an organic light emitting device comprising (9) and a cathode (4) is shown.

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 the anode material on the substrate in the reverse order of the above-described configuration from the cathode material (WO 2003/012890). 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 dopant. Here, the solution application 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.

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.

Hereinafter, preferred examples are presented to help the understanding of the present invention. However, the following examples are only provided for easier understanding of the present invention, and the content of the present invention is not limited thereto.

Synthesis Example 1-1: Synthesis of compound 1-1

Step 1) Synthesis of Intermediate A

11,12-dihydroindolo[2,3-a]carbazole (15.0g, 58.5mmol), 1-bromobenzene-2,3,4,5,6-d5 (10.4g, 64.4mmol), bis( tri-tert-butylphosphine)palladium(0) (Pd(Pt-Bu ₃ ) ₂ ) (0.6g, 1.2mmol), sodium tert-butoxide (NaOtBu)(8.4g, 87.8mmol), toluene 500ml, argon The mixture was stirred for 8 hours under reflux atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO4, concentrated, and the sample was purified by silica gel column chromatography to obtain 13.2 g of Intermediate A. (Yield 67%, MS[M+H]+=337)

Step 2) Synthesis of compound 1-1

Intermediate A (13.0 g, 38.5 mmol), compound a (14.6 g, 42.4 mmol), bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol), sodium tert-butoxide (5.6 g, 57.8 mmol), and 400 ml of xylene, and then stirred for 8 hours under reflux conditions in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H ₂ O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract _{was dried over MgSO 4} , concentrated, and the sample was purified by silica gel column chromatography, and then 7.9 g of compound 1-1 was obtained through sublimation purification. (Yield 32%, MS[M+H]+=644)

Synthesis example 1-2: Synthesis of compound 1-2

In step 1 of Synthesis Example 1-1, 1-bromobenzene-2,3,4,5,6-d5 was changed to bromobenzene to prepare intermediate B, and compound a was changed to compound b in step 2 Except that, compound 1-2 was prepared in the same manner as in the preparation method of compound 1-1. (MS[M+H] ⁺ = 644)

Synthesis Example 1-3: Synthesis of compound 1-3

Compound 1-3 was prepared in the same manner as in the preparation method of Compound 1-1, except that compound a was changed to compound c in step 2 of Synthesis Example 1-1. (MS[M+H] ⁺ = 649)

Synthesis Example 1-4: Synthesis of compound 1-4

In step 1 of Synthesis Example 1-1, 1-bromobenzene-2,3,4,5,6-d5 was changed to bromo-1,1'-biphenyl to prepare intermediate C, and in step 2, compound a Compound 1-4 was prepared in the same manner as in the preparation method of compound 1-1, except that was changed to compound d and used. (MS[M+H] ⁺ = 649)

Synthesis Example 1-5: Synthesis of compound 1-5

Step 1) Synthesis of Intermediate 1-5-1

Intermediate C (15.0 g, 36.7 mmol), compound e (13.9 g, 40.4 mmol), bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.7 mmol), sodium tert-butoxide (5.3 g, 55.1 mmol) and 400 ml of xylene were added, followed by stirring for 8 hours under reflux conditions in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H 2 O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract _{was dried over MgSO 4} , concentrated, and the sample was purified by silica gel column chromatography to obtain 17.1 g of Intermediate 1-5-1. (Yield 65%, MS[M+H]+= 715)

Step 2) Synthesis of compounds 1-5

Compound 1-5-1 (10.0 g, 14.0 _{mmol), PtO 2} (1.0 g, 4.2 mmol), and D2O 70ml were placed in a shaker tube, and then the tube was sealed and heated at 250° C., 600 psi for 12 hours. When the reaction was completed, chloroform was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract _{was dried over MgSO 4} , concentrated, and the sample was purified by silica gel column chromatography, and then 4.4 g of compound 1-5 was obtained through sublimation purification. (Yield 42%, deuterium substitution rate 82%, MS[M+H]+= 749)

Synthesis Example 1-6: Synthesis of compound 1-6

Compound 1-6 was prepared in the same manner as in the preparation method of Compound 1-1, except that in Step 2 of Synthesis Example 1-1, Intermediate A was changed to Intermediate B and Compound a was changed to Compound f. (MS[M+H] ⁺ = 658)

Synthesis Example 1-7: Synthesis of compound 1-7

1-bromobenzene-2,3,4,5,6-d5 in step 1 of Synthesis Example 1-1 to 2-bromodibenzo[b,d]furan-1,3,4,6,7,8,9-d7 Compound 1-7 was prepared in the same manner as in the preparation method of compound 1-1, except that Intermediate D was prepared by using , and compound a was changed to compound g in step 2 and used. (MS[M+H] ⁺ = 660)

Synthesis Example 1-8: Synthesis of compound 1-8

Compound 1-8 was prepared in the same manner as in the preparation method of Compound 1-1, except that in Step 2 of Synthesis Example 1-1, Intermediate A was changed to Intermediate B, and Compound a was changed to Compound h. (MS[M+H] ⁺ = 733)

Synthesis Example 1-9: Synthesis of compound 1-9

Except that 11,12-dihydroindolo [2,3-a] carbazole was changed to 5,8-dihydroindolo [2,3-c] carbazole in step 1 of Synthesis Example 1-1, the Compounds 1-9 were prepared by the same preparation method as the preparation method. (MS[M+H] ⁺ = 644)

Synthesis Example 1-10: Synthesis of compound 1-10

11,12-dihydroindolo[2,3-a]carbazole in step 1 of Synthesis Example 1-1 to 5,7-dihydroindolo[2,3-b]carbazole, 1-bromobenzene-2,3,4,5, Intermediate F was prepared by changing 6-d5 to bromobenzene, and compound 1-10 was prepared by the same preparation method as the preparation method of compound 1-1 except that compound a was changed to compound c in step 2 did. (MS[M+H] ⁺ = 644)

Synthesis Example 1-11: Synthesis of compound 1-11

Intermediate G was prepared by changing 11,12-dihydroindolo[2,3-a]carbazole to 5,11-dihydroindolo[3,2-b]carbazole in step 1 of Synthesis Example 1-1, and in step 2 Compound 1-11 was prepared in the same manner as in the preparation method of compound 1-1, except that compound a was changed to compound i and used. (MS[M+H] ⁺ = 674)

Synthesis Example 1-12: Synthesis of compound 1-12

Step 1) Synthesis of Intermediate H

5,12-dihydroindolo[3,2-a]carbazole (10.0 g, 39.0 mmol), compound j (16.7 g, 42.9 mmol), bis(tri-tert-butylphosphine) palladium(0) (0.4 g) in a 3-neck flask , 0.8mmol), sodium tert-butoxide (5.6g, 58.5mmol), and 400ml of toluene were added, followed by stirring for 8 hours under reflux conditions in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H ₂ O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract _{was dried over MgSO 4} , concentrated, and the sample was purified by silica gel column chromatography to obtain 16.9 g of Intermediate H. (Yield 71%, MS[M+H]+=608)

Step 2) Synthesis of compound 1-12

Intermediate H (15.0g, 24.6mmol), bromobenzene (4.3g, 27.1mmol), bis(tri-tert-butylphosphine)palladium(0) (0.3g, 0.5mmol), sodium tert-butoxide (3.6g) in a 3-neck flask , 37.0 mmol), and 250 ml of xylene were added, followed by stirring for 8 hours under reflux conditions in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H ₂ O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract _{was dried over MgSO 4} , concentrated, and the sample was purified by silica gel column chromatography, and then 5.4 g of Compound 1-12 was obtained through sublimation purification. (Yield 32%, MS[M+H]+=684)

Synthesis Example 1-13: Synthesis of compound 1-13

In step 1 of Synthesis Example 1-1, 11,12-dihydroindolo[2,3-a]carbazole to 5,12-dihydroindolo[3,2-a]carbazole, 1-bromobenzene-2,3,4,5 , 6-d5 was changed to bromobenzene to prepare Intermediate I, and Compound 1-13 was prepared in the same manner as in Compound 1-1, except that in step 2, compound a was changed to compound k. was prepared. (MS[M+H] ⁺ = 657)

Synthesis example 1-14: Synthesis of compound 1-14

In step 1 of Synthesis Example 1-1, 11,12-dihydroindolo[2,3-a]carbazole was replaced with 11,12-dihydroindolo[2,3-a]carbazole-1,3,5,6,8,10- Intermediate J was prepared using d6 and by changing 1-bromobenzene-2,3,4,5,6-d5 to 3-bromo-1,1':3',1''-terphenyl, step 2 Compound 1-14 was prepared in the same manner as in the preparation method of compound 1-1, except that compound a was changed to compound 1 in . (MS[M+H] ⁺ = 723)

Synthesis example 1-15: Synthesis of compound 1-15

In step 1 of Synthesis Example 1-1, 11,12-dihydroindolo[2,3-a]carbazole was replaced with 11,12-dihydroindolo[2,3-a]carbazole-1,2,3,4,5,6, Using 7,8,9,10-d10, and 1-bromobenzene-2,3,4,5,6-d5 changed to 3-bromo-1,1':3',1''-terphenyl Compound 1-15 was prepared by the same preparation method as that of compound 1-1, except that Intermediate K was prepared and compound a was changed to compound m in step 2 and used. (MS[M+H] ⁺ = 803)

Synthesis Example 2-1: Synthesis of compound 2-1

In a nitrogen atmosphere, 5,8-dihydroindolo[2,3-c]carbazole (15.0g, 58.5mmol) and 4-bromo-1,1'-biphenyl (30.0g, 128.8mmol) were added to 300ml of toluene, stirred and refluxed. . Then, sodium tert-butoxide (16.9g, 175.6mmol) and bis(tri-tert-butylphosphine)palladium(0) (0.9g, 1.8mmol) were added. After reaction for 12 hours, the mixture was cooled to room temperature, and the organic layer was separated using chloroform and water, and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. After the concentrated compound was purified by silica gel column chromatography, 9.8 g of compound 2-1 was prepared through sublimation purification. (Yield 30%, MS: [M+H]+= 562)

Synthesis Example 2-2: Synthesis of compound 2-2

Step 1) Synthesis of Intermediate 2-1-1

Toluene 5,8-dihydroindolo[2,3-c]carbazole (15.0 g, 58.5 mmol) and 4-bromo-1,1':4',1''-terphenyl (19.9 g, 64.4 mmol) in nitrogen atmosphere It was added to 300ml, stirred and refluxed. After that, sodium tert-butoxide (8.4g, 87.8mmol) and bis(tri-tert-butylphosphine)palladium(0) (0.9g, 1.8mmol) were added. After the reaction for 11 hours, the mixture was cooled to room temperature, the organic layer was separated using chloroform and water, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.3 g of Intermediate 2-2-1. (Yield 68%, MS: [M+H]+= 486)

Step 2) Synthesis of compound 2-2

Intermediate 2-2-1 (15.0 g, 31.0 mmol) and 3-bromo-1,1'-biphenyl (7.9 g, 34.0 mmol) were added to 300 ml of toluene in a nitrogen atmosphere, and stirred and refluxed. Then, sodium tert-butoxide (4.5g, 46.4mmol) and bis(tri-tert-butylphosphine)palladium(0) (0.5g, 0.9mmol) were added. After the reaction for 7 hours, it was cooled to room temperature, the organic layer was separated using chloroform and water, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. After the concentrated compound was purified by silica gel column chromatography, 9.5 g of compound 2-2 was prepared through sublimation purification. (Yield 48%, MS: [M+H]+= 638)

Synthesis Example 2-3: Synthesis of compound 2-3

In step 1 of Synthesis Example 2-2, 5,8-dihydroindolo[2,3-c]carbazole to 5,11-dihydroindolo[3,2-b]carbazole, 4-bromo-1,1':4',1''-terphenyl to 4-bromo-1,1'-biphenyl, 3-bromo-1,1'-biphenyl to 4-chloro-1,1':3',1''-terphenyl in step 2 Compound 2-3 was prepared in the same manner as in the preparation method of compound 2-2, except that it was changed to and used. (MS[M+H] ⁺ = 638)

Synthesis Example 2-4: Synthesis of compound 2-4

In step 1 of Synthesis Example 2-2, 5,8-dihydroindolo[2,3-c]carbazole to 5,12-dihydroindolo[3,2-a]carbazole, 4-bromo-1,1':4' , except that 1''-terphenyl was changed to 2-bromodibenzo[b,d]furan and 3-bromo-1,1'-biphenyl was changed to 4-bromo-1,1'-biphenyl in step 2 , Compound 2-4 was prepared by the same preparation method as that of compound 2-2. (MS[M+H] ⁺ = 576)

Example 1

A glass substrate coated with ITO (Indium Tin Oxide) to a thickness of 1,400 Å was placed in distilled water in which detergent was dissolved and washed with ultrasonic waves. At this time, a product manufactured by Fischer Co. was used as the detergent, and distilled water that was secondarily filtered with a filter manufactured by Millipore Co. was used as the distilled water. After washing ITO for 30 minutes, ultrasonic cleaning was performed for 10 minutes by repeating twice with distilled water. After washing with distilled water, ultrasonic washing was performed with a solvent of isopropyl alcohol, acetone, and methanol, dried, and then transported to a plasma cleaner. In addition, after cleaning the substrate for 5 minutes using oxygen plasma, the substrate was transported to a vacuum evaporator.

On the thus prepared ITO transparent electrode, the following HT-A and 5% by weight of PD were thermally vacuum deposited to a thickness of 100 Å to form a hole injection layer, and then only HT-A material was deposited to a thickness of 1150 Å to form a hole transport layer. The following HT-B was thermally vacuum-deposited to a thickness of 450 Å as an electron suppression layer thereon. Subsequently, compound 1-1 and compound 2-1 were vacuum-deposited to a thickness of 400 Å by using GD of 8 wt% of the host as a dopant in a weight ratio of 40:60 as a host of the emission layer. Then, the following ET-A was vacuum-deposited to a thickness of 50 Å as a hole blocking layer. Then, on the hole blocking layer, the following ET-B and Liq were thermally vacuum-deposited at a ratio of 2:1 to a thickness of 250 Å, and then LiF and magnesium were vacuum-deposited to a thickness of 30 Å at a ratio of 1:1, an electron transport layer and electron injection layers were sequentially formed. On the electron injection layer, magnesium and silver were deposited in a ratio of 1:4 to a thickness of 160 Å to form a cathode, thereby manufacturing an organic light emitting device.

Examples 2 to 23, and Comparative Examples 1 to 20

Organic light emitting devices of Examples 2 to 23 and Comparative Examples 1 to 20 were respectively manufactured in the same manner as in Example 1, except that the host material was changed as shown in Table 1 below. In this case, when a mixture of two types of compounds is used as the host, the weight ratio between the host compounds is indicated in parentheses.

Experimental example: device characteristic evaluation

Voltage, efficiency, and lifetime (T95) were measured by applying a current to the organic light-emitting devices manufactured in Examples and Comparative Examples, and the results are shown in Table 1 below. At this time, the voltage and efficiency were ^{measured by applying a current density of 10 mA/cm 2} , and T95 is the time (hr) until the initial luminance decreases to 95% at a current density of 20 mA/cm ^{2 .}

host
matter @ 10mA/cm ² @ 20mA/cm ² Voltage
(V) efficiency
(cd/A) life span
(T95, hr) Example 1 Compound 1-1: Compound 2-1
(40:60) 4.01 64.1 132 Example 2 Compound 1-2: Compound 2-1 (40: 60) 4.00 64.1 135 Example 3 Compound 1-3: Compound 2-1 (40: 60) 4.01 64.2 143 Example 4 Compound 1-4: Compound 2-1 (40:60) 4.08 62.2 138 Example 5 Compound 1-5: Compound 2-1 (40:60) 4.02 64.3 152 Example 6 Compound 1-6: Compound 2-1 (40: 60) 4.07 64.7 145 Example 7 Compound 1-7: Compound 2-1 (40:60) 4.08 64.2 130 Example 8 Compound 1-8: Compound 2-1 (40: 60) 4.05 64.1 128 Example 9 Compound 1-9: Compound 2-1 (40: 60) 4.17 63.7 133 Example 10 Compound 1-10: Compound 2-1 (40: 60) 4.16 64.2 130 Example 11 Compound 1-11: Compound 2-1 (40:60) 4.13 63.8 131 Example 12 Compound 1-12: Compound 2-1 (40: 60) 4.19 64.7 127 Example 13 Compound 1-13: Compound 2-1 (40: 60) 4.21 62.9 137 Example 14 Compound 1-14: Compound 2-1 (40: 60) 4.03 65.1 138 Example 15 Compound 1-15: Compound 2-1 (40:60) 4.07 64.9 141 Example 16 Compound 1-1: Compound 2-2 (40:60) 4.03 64.6 135 Example 17 Compound 1-2: Compound 2-2 (40:60) 4.02 64.5 130 Example 18 Compound 1-2: Compound 2-3 (40: 60) 4.07 63.1 122 Example 19 Compound 1-3: Compound 2-3 (40:60) 4.08 63.2 128 Example 20 Compound 1-4: Compound 2-3 (40: 60) 4.09 63.3 125 Example 21 Compound 1-5: Compound 2-4 (40:60) 4.11 64.1 141 Example 22 Compound 1-6: Compound 2-4 (40:60) 4.18 64.0 130 Example 23 Compound 1-10: Compound 2-4 (30:70) 4.21 63.1 119 Comparative Example 1 compound 1-1 4.71 54.1 91 Comparative Example 2 compound 1-6 4.67 52.7 84 Comparative Example 3 compound 2-1 7.62 7.5 5 Comparative Example 4 compound 2-3 7.82 5.8 3 Comparative Example 5 Compound GH-1-A: Compound 2-1 (40:60) 4.02 62.5 82 Comparative Example 6 Compound GH-1-B: Compound 2-1 (40:60) 4.23 61.7 71 Comparative Example 7 Compound GH-1-C: Compound 2-1 (40:60) 4.65 56.6 85 Comparative Example 8 Compound GH-1-A: Compound 2-2 (40:60) 4.07 62.3 86 Comparative Example 9 Compound GH-1-B: Compound 2-3 (40:60) 4.35 58.2 65 Comparative Example 10 Compound 1-1: Compound GH-2-A (40:60) 4.51 56.6 90 Comparative Example 11 Compound 1-1: Compound GH-2-B (40:60) 4.57 57.7 92 Comparative Example 12 Compound 1-1: Compound GH-2-C (40:60) 4.48 55.7 93 Comparative Example 13 Compound 1-6: Compound GH-2-B (40:60) 4.51 56.5 103 Comparative Example 14 Compound GH-1-A: Compound GH-2-D (40:60) 4.02 62.5 82 Comparative Example 15 Compound 1-1: Compound GH-2-E (40:60) 5.51 31.0 21 Comparative Example 16 Compound 1-1: Compound GH-2-F (40:60) 5.23 42.3 40 Comparative Example 17 Compound 1-1: Compound GH-2-G (40:60) 5.07 44.5 51 Comparative Example 18 Compound GH-1-A 4.71 54.2 60 Comparative Example 19 Compound GH-1-B 4.83 50.3 53 Comparative Example 20 Compound GH-2-A 7.76 6.7 8

In the present invention, the first compound represented by Formula 1 and the second compound represented by Formula 2 both have an indolocarbazole skeleton. Here, the first compound has a strong ability to transport electrons including a triazine group, and the second compound has a strong ability to transport holes, so it has suitable properties for using a mixture of two materials as a host. In particular, since both materials have an indolocarbazole structure, they are mixed well to form an exciplex and are advantageous in effectively transferring energy to a dopant. At this time, the first compound becomes an anion and the second compound becomes a cation to form an exciplex, but the first compound that becomes an anion state has a more unstable state. By substituting 5 or more of deuterium here, the vibration energy of the first compound is lowered even in an anion state and has more stable energy.

As a result, as can be seen in Table 1, Examples 1 to 23 using the first compound represented by Formula 1 and the second compound represented by Formula 2 together as a light emitting layer of an organic electroluminescent device in the present invention are Comparative Examples It showed significantly improved low-voltage, high-efficiency, and long-life characteristics compared to the above.

1: Substrate 2: Anode
3: light emitting layer 4: cathode
5: hole injection layer 6: hole transport layer
7: electron blocking layer 8: hole blocking layer
9: Electron injection and electron transport layer

Claims (15)

an anode, a cathode, and a light emitting layer between the anode and the cathode;
The light emitting layer comprises a first compound represented by the following formula (1) and a second compound represented by the following formula (2),
Organic light emitting device:
[Formula 1]

In Formula 1,
A is a benzene ring fused with two adjacent pentagonal rings each,
Ar ₁ to Ar ₃ are each independently substituted or unsubstituted C _6-60 aryl; _{Or a substituted or unsubstituted C 5-60} heteroaryl containing any one or more heteroatoms selected from the group consisting of N, O and S;
R ₁ is each independently hydrogen; heavy hydrogen; halogen; cyano; substituted or unsubstituted C _1-60 alkyl; substituted or unsubstituted C _1-60 alkoxy; substituted or unsubstituted C _2-60 alkenyl; substituted or unsubstituted C _2-60 alkynyl; substituted or unsubstituted C _3-60 cycloalkyl; substituted or unsubstituted C _6-60 aryl; _{Or substituted or unsubstituted C 2-60} heteroaryl containing any one or more heteroatoms selected from the group consisting of N, O and S,
x is an integer from 1 to 10,
provided _{that at least one of Ar 1} to Ar ₃ , and R ₁ is substituted with one or more deuterium, or _{at least one of R 1} is deuterium, and the first compound contains at least 5 deuterium,
[Formula 2]

In Formula 2,
B is a benzene ring fused with two adjacent pentagonal rings, respectively,
Ar ₄ is a substituted or unsubstituted C _6-60 aryl,
Ar ₅ is substituted or unsubstituted C _6-60 aryl; _{Or a substituted or unsubstituted C 5-60} heteroaryl containing one heteroatom selected from the group consisting of N, O and S,
R ₂ are each independently hydrogen; heavy hydrogen; halogen; cyano; substituted or unsubstituted C _1-60 alkyl; substituted or unsubstituted C _1-60 alkoxy; substituted or unsubstituted C _2-60 alkenyl; substituted or unsubstituted C _2-60 alkynyl; substituted or unsubstituted C _3-60 cycloalkyl; substituted or unsubstituted C _6-60 aryl; _{Or substituted or unsubstituted C 2-60} heteroaryl containing any one or more heteroatoms selected from the group consisting of N, O and S,
y is an integer from 1 to 10;
According to claim 1,
Formula 1 is represented by any one selected from the group consisting of the following Formulas 1-1 to 1-6,
Organic light emitting device:
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Formula 1-6]

In Formulas 1-1 to 1-6, Ar ₁ to Ar ₃ , R ₁ , and x are as defined in claim 1.
According to claim 1,
Ar _{1 To} Ar ₃ are each independently phenyl, biphenyl, terphenyl, dibenzofuranyl, dibenzothiophenyl, fluorenyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl , carbazol-9-yl, or 9-phenyl-9H-carbazolyl;
organic light emitting device.
According to claim 1,
At least one of Ar ₁ to Ar _{3 is phenyl,}
The rest are each independently phenyl, biphenyl, terphenyl, dibenzofuranyl, dibenzothiophenyl, fluorenyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, carbazole- 9-yl, or 9-phenyl-9H-carbazolyl;
organic light emitting device.
According to claim 1,
At least one of Ar ₁ to Ar ₃ is phenyl substituted with 5 deuterium,
The rest are unsubstituted, phenyl, biphenyl, terphenyl, dibenzofuranyl, dibenzothiophenyl, fluorenyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, carbazole -9-yl, or 9-phenyl-9H-carbazolyl;
organic light emitting device.
According to claim 1,
One of Ar ₁ to Ar ₃ is biphenyl, terphenyl, dibenzofuranyl, dibenzothiophenyl, fluorenyl, 9,9-dimethylfluorenyl, 9,9 substituted with 5 or more deuterium -diphenylfluorenyl, carbazol-9-yl, or 9-phenyl-9H-carbazolyl;
The rest are each independently unsubstituted phenyl or unsubstituted biphenyl,
organic light emitting device.
According to claim 1,
Ar _{1 To} Ar ₃ are each independently phenyl, biphenyl, terphenyl, dibenzofuranyl, dibenzothiophenyl, fluorenyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl , carbazol-9-yl, or 9-phenyl-9H-carbazolyl,
The Ar _{One To} Ar ₃ All are completely substituted with deuterium,
organic light emitting device.
According to claim 1,
The R ₁ is all hydrogen,
organic light emitting device.
According to claim 1,
At least 5 of R ₁ are deuterium, the rest are hydrogen,
organic light emitting device.
According to claim 1,
The first compound is any one selected from the group consisting of
Organic light emitting device:

.
According to claim 1,
Formula 2 is represented by any one selected from the group consisting of the following Formulas 2-1 to 2-6,
Organic light emitting device:
[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Formula 2-4]

[Formula 2-5]

[Formula 2-6]

In Formulas 2-1 to 2-6, Ar ₄ , Ar ₅ , R ₂ , and y are as defined in claim 1.
According to claim 1,
Ar ₄ and Ar ₅ are each independently unsubstituted, phenyl, biphenyl, terphenyl, fluorenyl, 9,9-dimethylfluorenyl, or 9,9-diphenylfluorenyl;
organic light emitting device.
According to claim 1,
Ar ₄ is unsubstituted, phenyl, biphenyl or terphenyl,
Ar ₅ is unsubstituted, dibenzofuranyl, dibenzothiophenyl, carbazol-9-yl, or 9-phenyl-9H-carbazolyl;
organic light emitting device.
According to claim 1,
R ₂ are all hydrogen,
organic light emitting device.
According to claim 1,
The second compound is any one selected from the group consisting of
Organic light emitting device:

.

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