KR102446400B1 - 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.

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, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, it may be made of an electron injection layer, etc. When a voltage is applied between the two electrodes in the structure of the organic light emitting device, 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 It lights up when it falls back to the ground state.

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.

The present invention provides the following organic light emitting device:

anode;

a negative electrode provided to face the positive electrode; and

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

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

[Formula 1]

In Formula 1,

X is O or S;

X ₁ to X ₃ are each independently N or CH, provided that at least one of X ₁ to X ₃ is N,

Ar ₁ and Ar ₂ are each independently, substituted or unsubstituted C _6-60 aryl; substituted or unsubstituted C _2-60 heteroaryl comprising one or more heteroatoms of N, O and S, wherein at least one of the heteroatoms is N; or C _2-60 heteroaryl comprising heteroatoms O or S unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium, halogen, cyano and nitro;

R ₁ to R ₃ are each independently hydrogen; heavy hydrogen; halogen; cyano; nitro; amino; substituted or unsubstituted C _1-60 alkyl; substituted or unsubstituted C _3-60 cycloalkyl; substituted or unsubstituted C _2-60 alkenyl; substituted or unsubstituted C _6-60 aryl; or C _2-60 heteroaryl containing one or more heteroatoms among substituted or unsubstituted N, O and S;

a+b is an integer from 0 to 6,

c is an integer from 0 to 8;

[Formula 2]

In Formula 2,

Y is O or S;

Ar ₃ is substituted or unsubstituted C _6-60 aryl; or C _2-60 heteroaryl containing one or more heteroatoms among substituted or unsubstituted N, O and S;

R ₄ to R ₆ are each independently hydrogen; heavy hydrogen; halogen; cyano; nitro; amino; substituted or unsubstituted C _1-60 alkyl; substituted or unsubstituted C _3-60 cycloalkyl; substituted or unsubstituted C _2-60 alkenyl; substituted or unsubstituted C _6-60 aryl; or C _2-60 heteroaryl containing one or more heteroatoms among substituted or unsubstituted N, O and S;

d, e and f are each independently an integer from 0 to 7,

When a, b, c, d, e and f are each 2 or more, the substituents in parentheses are the same as or different from each other.

In the above-described organic light emitting device, efficiency, driving voltage, and/or lifespan characteristics may be improved in the organic light emitting device by including two kinds of host compounds in the light emitting layer.

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 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 transport and injection layer An example of an organic light emitting device comprising (8) and a cathode (4) is shown.

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

, 또는

는 다른 치환기에 연결되는 결합을 의미하고, D는 중수소를 의미하고, Ph는 페닐기를 의미한다. In this specification,

, or

denotes a bond connected to another substituent, D denotes deuterium, and Ph denotes a phenyl group.

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 aryl phosphine 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, or substituted or unsubstituted, in which two or more substituents of the above-exemplified substituents are connected . 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 of the carbonyl group is not particularly limited, but it is preferably from 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 a trimethylboron group, a triethylboron group, a t-butyldimethylboron group, a triphenylboron group, a phenylboron group, and the like, but is not limited thereto.

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

In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to an exemplary embodiment, the 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 is 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 is 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 heteroaryl group is a heterocyclic group including one or more heteroatoms among O, N, Si and S as a heterogeneous element, and the number of carbon atoms is not particularly limited, but is preferably from 2 to 60 carbon atoms. Examples of the heteroaryl 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, the arylamine group, and the arylsilyl group is the same as the examples 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 examples of the above-described alkenyl groups. 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 aforementioned heteroaryl 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.

anode; a negative electrode provided to face the positive electrode; and a light emitting layer provided between the anode and the cathode, wherein the light emitting layer includes a first compound represented by Formula 1 and a second compound represented by Formula 2 above.

The organic light emitting device according to the present invention may include two types of compounds having a specific structure as a host material in the light emitting layer at the same time, thereby improving efficiency, driving voltage, and/or lifespan characteristics in the organic light emitting device.

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

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; A multi-layered 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 include a hole injection layer between the anode and the hole transport layer to be described later, if necessary.

The hole injection layer is located on the anode and injects holes from the anode, and includes a hole injection material. Such a hole injection material has the ability to transport holes, has a hole injection effect at the anode, an excellent hole injection effect on the light emitting layer or the light emitting material, and prevents the movement of excitons generated in the light emitting layer to the electron injection layer or the electron injection material. In addition, a compound excellent in the ability to form a thin film is preferable. In particular, it is suitable 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. organic materials, anthraquinone, 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 between the anode and the light emitting layer. The hole transport layer receives holes from the anode or the hole injection layer formed on the anode and transports holes to the light emitting layer, and includes a hole transport material. As the hole transport material, a material capable of transporting holes from an anode or a hole injection layer to the light emitting layer is suitable, and a material having high hole mobility 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.

electronic barrier layer

The organic light emitting diode according to the present invention may include an electron blocking layer between the hole transport layer and the light emitting layer, if necessary. The electron blocking layer is formed on the hole transport layer, preferably provided in contact with the light emitting layer, to control hole mobility and prevent excessive movement of electrons to increase the probability of hole-electron coupling by increasing the efficiency of the organic light emitting device It means a layer that plays a role in improving The electron blocking layer includes an electron blocking material, and an example of such an electron blocking material may be an arylamine-based organic material, but is not limited thereto.

light emitting layer

The organic light emitting diode according to the present invention includes a light emitting layer between an anode and a cathode, and the light emitting layer includes the first compound and the second compound as a host material. Specifically, the first compound functions as an N-type host material having an electron transporting ability superior to a hole transporting ability, and the second compound functions as a P-type host material having a hole transporting ability superior to an electron transporting ability. The ratio of electrons to electrons can be properly maintained. Accordingly, excitons may emit light evenly throughout the light emitting layer, thereby improving luminous efficiency and lifetime characteristics of the organic light emitting diode.

Hereinafter, the first compound and the second compound will be sequentially described.

(first compound)

The first compound is represented by Formula 1 above. Specifically, the first compound is a compound in which a carbazolyl group and an N-containing 6-membered-heterocyclic group are simultaneously substituted on the dibenzofuran/dibenzothiophene core, and this compound has an intramolecular charge compared to a compound not having all of these substituents. Molecular stability is high because inter charge transfer is well performed, and hole and electron transport can be performed effectively. In addition, this effect can be further maximized when the second compound, which will be described later, is used together as a host of the light emitting layer.

In addition, the first compound may not contain deuterium in the molecule.

Alternatively, the first compound may include at least one deuterium. In this case, in Formula 1, at least one of Ar ₁ and Ar ₂ is C _6-60 aryl substituted with deuterium; or C _2-60 heteroaryl comprising one or more heteroatoms of N, O and S substituted with deuterium; or at least one of R ₁ to R ₃ is deuterium; C _6-60 aryl substituted with deuterium; or C _2-60 heteroaryl containing at least one heteroatom among N, O and S substituted with deuterium, and a+b+c may be 1 or more, or an integer of 1 to 14.

Alternatively, C _6-60 aryl in which at least one of Ar ₁ and Ar ₂ is substituted with deuterium; or C _2-60 heteroaryl containing one or more heteroatoms among N, O and S substituted with deuterium, wherein at least one of R ₁ to R ₃ is deuterium; C _6-60 aryl substituted with deuterium; or C _2-60 heteroaryl containing one or more heteroatoms among N, O and S substituted with deuterium, and a+b+c may be one or more.

In this case, the first compound may be represented by the following Chemical Formula 1':

[Formula 1']

In Formula 1',

이고, 나머지는 각각 독립적으로 R₂의 정의를 참조하고, R₁₁ 내지 R₁₄ 중 하나가

이고, 나머지는 각각 독립적으로 R₁의 정의를 참조하거나, 또는One of R ₂₁ to R ₂₄ is

and the rest each independently refer to the definition of R ₂ , and one of R ₁₁ to R ₁₄ is

and the rest each independently refer to the definition of R ₁ , or

이고, R₁₁ 내지 R₁₃ 중 하나가

이고, 나머지는 각각 독립적으로 R₁의 정의를 참조한다.R ₂₁ to R ₂₄ each independently refer to the definition of R ₂ , and R ₁₄ is

and one of R ₁₁ to R ₁₃ is

, and the rest refer to the definition of R ₁ independently of each other.

In addition, when the first compound is represented by Formula 1', it may be more advantageous in terms of intramolecular charge transfer and molecular stability than a compound in which a carbazolyl group and a 6-membered N-containing heterocyclic group are substituted at other positions. .

More specifically, the first compound may be represented by any one of the following Chemical Formulas 1A' to 1E':

[Formula 1A']

[Formula 1B']

[Formula 1C']

[Formula 1D']

[Formula 1E']

In the formulas 1A' to 1E',

X, X ₁ to X ₃ , Ar ₁ , Ar ₂ , R ₁ to R ₃ , a+b and c are as defined in Formula 1 above.

In this case, in Formulas 1A' to 1D', a and b are each an integer of 0 to 3,

In Formula 1E', a is an integer from 0 to 2, and b is an integer from 0 to 4.

More specifically, the compound represented by Formula 1C 'is the following Formula 1A (position 6 of the core), Formula 1B (position 7 of the core), Formula 1C depending on the substitution position of the N-containing 6-membered-heterocyclic group (position 8 of the core), or Formula 1D (position 9 of the core):

[Formula 1A]

[Formula 1B]

[Formula 1C]

[Formula 1D]

In Formulas 1A to 1D,

a and b are each an integer from 0 to 3,

The description of the remaining substituents is as defined in Formula 1 above.

Preferably, X is O.

Preferably, X ₁ to X ₃ are all N,

X ₁ and X ₂ are N and X ₃ is CH,

X ₁ and X ₃ are N and X ₂ is CH,

X ₁ is N, X ₂ and X ₃ are CH, or

X ₂ may be N, and X ₁ and X ₃ may be CH.

Preferably, Ar ₁ and Ar ₂ are each independently C _6-20 unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium, C _1-10 alkyl and C _6-20 aryl. aryl; containing one or two heteroatoms of N, O and S, unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium, C _1-10 alkyl and C _6-20 aryl; C _2-20 heteroaryl wherein at least one of the heteroatoms is N; or C _2-60 heteroaryl comprising heteroatoms O or S unsubstituted or substituted with deuterium.

That is, Ar ₁ and Ar ₂ may not include C _2-60 heteroaryl including heteroatoms O or S substituted with C _6-20 aryl. Specifically, Ar ₁ and Ar ₂ do not include dibenzofuranyl substituted with phenyl and dibenzothiophenyl substituted with phenyl, but these structures have improved intramolecular charge transfer and molecular weight compared to the structure represented by Formula 1 herein. This is because it may be disadvantageous in terms of stability.

More preferably, Ar ₁ and Ar ₂ are each independently phenyl, biphenylyl, naphthyl, unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium and C _6-20 aryl , phenanthryl, carbazolyl, benzoxazolyl, or benzothiazolyl; dibenzofuranyl unsubstituted or substituted with deuterium; or dibenzothiophenyl unsubstituted or substituted with deuterium.

More preferably, Ar ₁ and Ar ₂ are each independently phenyl, biphenylyl, naphthyl, phenanthryl, unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium and phenyl; carbazolyl, benzoxazolyl, or benzothiazolyl; dibenzofuranyl unsubstituted or substituted with deuterium; or dibenzothiophenyl unsubstituted or substituted with deuterium.

In this case, when Ar ₁ and Ar ₂ are substituted with deuterium, all hydrogens in the molecules of Ar ₁ and Ar ₂ may be substituted with deuterium.

For example, Ar ₁ and Ar ₂ may be any one selected from the group consisting of, but are not limited thereto:

above,

m is an integer from 0 to 7.

, 또는

일 수 있다.In addition, at least one of Ar ₁ and Ar ₂ is

, or

can be

Also, Ar ₁ and Ar ₂ may be the same as each other. Or Ar ₁ and Ar ₂ may be different.

Preferably, R ₁ to R ₃ are each independently, deuterium; C _6-20 aryl unsubstituted or substituted with deuterium; or C _2-20 heteroaryl comprising one heteroatom of N, O and S unsubstituted or substituted with deuterium.

Preferably, R ₁ and R ₂ may each independently be hydrogen, deuterium, phenyl, phenyl substituted with 1 to 5 deuterium, carbazolyl, dibenzofuranyl, or dibenzothiophenyl.

In addition, R ₃ is hydrogen; heavy hydrogen; phenyl unsubstituted or substituted with deuterium; carbazolyl unsubstituted or substituted with deuterium; dibenzofuranyl unsubstituted or substituted with deuterium; or dibenzothiophenyl unsubstituted or substituted with deuterium.

는 하기 화학식 3a 내지 3i로 표시되는 치환기 중 어느 하나일 수 있다:In addition, the substituent of Formula 1

may be any one of the substituents represented by the following formulas 3a to 3i:

In Formulas 3a to 3i,

p is an integer from 0 to 7,

q is an integer from 0 to 8;

In addition, in Formula 1, a+b meaning the sum of the number of R ₁ and R ₂ may be 0, 1, 2, 3, 4, 5, or 6, and c meaning the number of R ₃ is 0, 1, 2, 3, 4, 5, 6, 7, or 8.

Preferably, a+b is 0, 1, 2, or 6, and c may be 0, 1, 2, or 8. In this case, when a+b is 6, both R ₁ and R ₂ may be deuterium, and when c is 8, R ₃ may be deuterium.

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

.

Meanwhile, the compound represented by Formula 1 may be prepared by, for example, a preparation method as shown in Scheme 1 below. The manufacturing method may be more specific in Preparation Examples to be described later.

[Scheme 1]

In Scheme 3, X _a and X' are each independently halogen, preferably X _a is fluoro, X' is bromo or chloro, and definitions of other substituents are the same as described above.

Specifically, the compound represented by Formula 1 may be prepared through steps 1-1 and 1-2.

Step 1-1 is a step of preparing the intermediate compound A3 through the Suzuki-coupling reaction of the starting materials A1 and A2. The Suzuki-coupling reaction is preferably performed in the presence of a palladium catalyst and a base, respectively, and the reactor for the Suzuki-coupling reaction may be appropriately changed.

In addition, step 1-2 is a step of preparing a compound represented by Formula 1 in which a carbazole group is introduced into the intermediate compound A3 through an amine substitution reaction between the intermediate compound A3 and the compound A4, and this amine substitution reaction is performed with a palladium catalyst It is preferred to carry out in the presence of a base. In addition, the reactive group for the amine substitution reaction may also be appropriately modified as known in the art.

The method for preparing the compound represented by Formula 1 may be more specific in Preparation Examples to be described later.

(second compound)

The second compound is represented by Formula 2 above. Specifically, the second compound is a compound in which one N atom of biscarbazole is substituted with dibenzofuranyl or dibenzothiophenyl. In particular, since the second compound has excellent hole properties in the biscarbazole structure, electron transport properties may be controlled by substituting an Ar ₃ substituent based on the indolocarbazole structure. Accordingly, when the second compound is used together with the first compound in the light emitting layer, hole and electron transport properties can be variously adjusted, which is advantageous in balancing the charge in the light emitting layer.

The second compound may be represented by any one of the following formulas 2A to 2D according to the substitution position of dibenzofuranyl/dibenzothiophenyl:

[Formula 2A]

[Formula 2B]

[Formula 2C]

[Formula 2D]

In Formulas 2A to 2D,

Y, Ar ₃ , R ₄ to R ₆ , d, e and f are as defined in Formula 2 above.

Preferably, Ar ₃ is C _6-20 aryl; or C _2-20 heteroaryl comprising one or two heteroatoms of N, O and S;

Here, Ar ₃ may be unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium, C _6-20 aryl, and C _6-20 aryl substituted with deuterium.

More preferably, Ar ₃ is phenyl, biphenylyl, naphthyl, phenanthrenyl, triphenylenyl, carbazolyl, dibenzofuranyl, dibenzothiophenyl, benzoxazolyl, or benzothiazolyl,

Here, Ar ₃ may be unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium, C _6-20 aryl, and C _6-20 aryl substituted with deuterium.

More preferably, Ar ₃ is phenyl, biphenylyl, naphthyl, phenanthrenyl, triphenylenyl, carbazolyl, dibenzofuranyl, dibenzothiophenyl, benzoxazolyl, or benzothiazolyl,

Here, Ar ₃ may be unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium, phenyl, and phenyl substituted with deuterium.

For example, Ar ₃ may be any one selected from the group consisting of, but is not limited thereto:

Preferably, R ₄ to R ₆ are each independently, deuterium; It may be unsubstituted or substituted C _6-20 aryl with deuterium.

More preferably, R ₄ to R ₆ may each independently be deuterium, or phenyl unsubstituted or substituted with deuterium.

일 수 있으나, 이에 한정되는 것은 아니다. For example, R ₄ to R ₆ are each independently, deuterium, phenyl, or

may be, but is not limited thereto.

In addition, in Formula 2, d meaning the number of R ₄ , e meaning the number of R ₅ , and f meaning the number of R ₆ are each independently 0, 1, 2, 3, 4, 5, 6 , or 7 .

Preferably, d, e and f can each independently be 0, 1, or 7. In this case, when d, e and f are 7, R ₄ to R ₆ may each be deuterium.

In addition, the second compound may be represented by any one of the following Chemical Formulas 2-1 to 2-4:

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Formula 2-4]

In Formulas 2-1 to 2-4,

D means deuterium,

Y, Ar ₃ , R ₆ and f are as defined in Formula 2 above.

On the other hand, representative examples of the compound represented by Formula 2 are as follows:

Meanwhile, the compound represented by Formula 2 may be prepared by, for example, a preparation method as shown in Scheme 2 below. The manufacturing method may be more specific in Preparation Examples to be described later.

[Scheme 2]

In Scheme 2, X" is halogen, preferably bromo, or chloro, and definitions of other substituents are as described above.

Specifically, the compound represented by Formula 2 is prepared by combining starting materials B1 and B2 through an amine substitution reaction. These amine substitution reactions are preferably performed in the presence of a palladium catalyst and a base, respectively. In addition, the reactive group for the amine substitution reaction may be appropriately changed, and the method for preparing the compound represented by Formula 2 may be more specific in Preparation Examples to be described later.

Also, the first compound and the second compound may be included in a weight ratio of 1:9 to 9:1 in the emission layer. When the first compound is included in an excessively small amount in the light emitting layer, electron transport in the light emitting layer is not smooth, so that the overall balance of holes and electrons in the device becomes out of balance, and there may be problems in voltage, efficiency and lifespan of the manufactured device, When the second compound is included in an excessively small amount compared to the first compound in the light emitting layer, there may be a problem in that the lifespan is reduced. For example, a weight ratio of the first compound and the second compound in the emission layer is 2:8 to 8:2, 3:7 to 7:3, 4:6 to 6:4, or 4:6 to 5:5 can be

Meanwhile, the emission layer may further include a dopant material in addition to the two types of host materials. Examples of the dopant material 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. As the styrylamine compound, a substituted or unsubstituted 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 an iridium complex, a platinum complex, and the like, but is not limited thereto.

hole blocking layer

The organic light emitting diode according to the present invention may include a hole blocking layer between the light emitting layer and the electron transport layer to be described later, if necessary. The hole blocking layer is formed on the light emitting layer, preferably provided in contact with the light emitting layer, to improve the efficiency of the organic light emitting device by controlling electron mobility and preventing excessive movement of holes to increase the hole-electron coupling probability layer that plays a role. The hole blocking layer includes a hole blocking material, and examples of the hole blocking material include azine derivatives including triazine; triazole derivatives; oxadiazole derivatives; phenanthroline derivatives; A compound into which an electron withdrawing group is introduced, such as a phosphine oxide derivative, may be used, but the present invention is not limited thereto.

In this case, the dopant material may be included in an amount of 1 to 25% by weight based on the total weight of the host material (the sum of the weight of the compound represented by Formula 1 and the compound represented by Formula 2) and the dopant material in the light emitting layer. have.

electron transport layer

The electron transport layer is formed between the light emitting layer and the cathode to receive electrons from the electron injection layer and transport the electrons to the light emitting layer. The electron transport layer includes an electron transport material. As the electron transport material, a material capable of receiving electrons from the cathode and transferring them to the light emitting layer is suitable, and a material having high electron mobility is suitable.

Specific examples of the electron injection and transport material include Al complex of 8-hydroxyquinoline; complexes containing Alq ₃ ; organic radical compounds; hydroxyflavone-metal complexes; and triazine derivatives, but is not limited thereto. or fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone, and derivatives thereof, metal complex compounds , or may be used together with a nitrogen-containing 5-membered ring derivative, and the like, but is not limited thereto.

electron transport and injection layer

The organic light emitting diode according to the present invention may include an electron injection layer between the electron transport layer and the cathode, if necessary. Alternatively, the organic light emitting device may include an electron transport and injection layer, if necessary.

The electron transport and injection layer is a layer that simultaneously serves as an electron transport layer and an electron injection layer for injecting electrons from the electrode and transporting the received electrons to the emission layer, and is formed on the emission layer or the hole blocking layer. As the electron injection and transport material, a material capable of receiving electrons from the cathode and transferring them to the light emitting layer is suitable, and a material having high electron mobility is suitable. Specific examples of the electron injection and transport material include Al complex of 8-hydroxyquinoline; complexes containing Alq ₃ ; organic radical compounds; hydroxyflavone-metal complexes; and triazine derivatives, but is not limited thereto. or fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, fluorenylidene methane, anthrone, and derivatives thereof, metal complex compounds , or may be used together with a nitrogen-containing 5-membered ring derivative, and the like, but is not limited thereto.

The electron transport and injection layer may also be formed as a separate layer such as an electron injection layer and an electron transport layer. In this case, the electron transport layer is formed on the emission layer or the hole blocking layer, and the electron injection and transport material described above may be used as the electron transport material included in the electron transport layer. In addition, the electron injection layer is formed on the electron transport layer, and the electron injection material included in the electron injection layer is LiF, NaCl, CsF, Li ₂ O, BaO, fluorenone, anthraquinodimethane, diphenoquinone, Thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, benzimidazole, perylene tetracarboxylic acid, preorenylidene methane, anthrone and their derivatives, metal complex compounds, nitrogen-containing 5-membered ring derivatives, etc. may be used can

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 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 , and a cathode 4 . In such a structure, the first compound and the second compound may be included in the emission layer.

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 transport and injection layer An example of an organic light emitting device comprising (8) and a cathode (4) is shown. In such a structure, the first compound and the second compound may be included in the emission layer.

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

Meanwhile, the organic light emitting device according to the present invention may be a top emission type, a back emission type, or a double side 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 intended to illustrate the present invention, and the scope of the present invention is not limited thereto.

[Synthesis Example]

Synthesis Example 1: Synthesis of compound 1-1

Step 1) Synthesis of compound 1-1-a

In a nitrogen atmosphere, 2-bromo-5-chlorophenol (20 g, 96.4 mmol) and (2,6-difluorophenyl) boronic acid (15.2 g, 96.4 mmol) were added to 400 ml of tetrahydrofuran, stirred and refluxed. . Thereafter, sodium carbonate (30.7 g, 289.2 mmol) was dissolved in 31 ml of water, and after stirring sufficiently, tetrakistriphenyl-phosphinopalladium (3.3 g, 2.9 mmol) was added. After the reaction for 3 hours, after cooling to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again put into 464 mL of chloroform 20 times to dissolve, 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 recrystallized from chloroform and ethyl acetate to prepare a white solid compound 1-1-a (16.5 g, 71%, MS: [M+H] + = 241.6).

Step 2) Synthesis of compound 1-1-b

1-1-a (15 g, 62.3 mmol) and 0 (15.2 g, 62.3 mmol) and potassium carboenite (25.8 g, 187 mmol) were added, put into 300 ml of dimethylformamide, and stirred and refluxed. After the reaction for 3 hours, the resulting solid was filtered after cooling to room temperature. The solid was dissolved in 30 times 413 mL of 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 through a silica column using chloroform and ethyl acetate to prepare a white solid compound 1-1-b (10.7 g, 78%, MS: [M+H] + = 221.6).

Step 3) Synthesis of compound 1-1-c

In a nitrogen atmosphere, 1-1-b (20 g, 90.6 mmol) and bis (pinacolato) diboron (23 g, 90.6 mmol) were added to 400 ml of Diox, stirred and refluxed. After that, potassium triphosphate (57.7 g, 271.9 mmol) was added and sufficiently stirred, palladium dibenzylideneacetone palladium (1.6 g, 2.7 mmol) and tricyclohexylphosphine (1.5 g, 5.4 mmol) were added. After the reaction for 2 hours, after cooling to room temperature, the organic layer was filtered to remove salt, and the filtered organic layer was distilled. This was again put in 283 mL of chloroform 10 times to dissolve, 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 recrystallized from chloroform and ethanol to prepare a brown solid compound 1-1-c (22.6 g, 80%, MS: [M+H] + = 313.2).

Step 4) Synthesis of compound 1-1-d

1-c (20 g, 64.1 mmol) and 2-chloro-4- (dibenzo [b,d] furan-3-yl) -6-phenyl-1,3,5-triazine (22.9 g) in a nitrogen atmosphere , 64.1 mmol) was added to 400 ml of tetrahydrofuran, stirred and refluxed. Thereafter, sodium carbonate (20.4 g, 192.2 mmol) was dissolved in 20 ml of water, and after stirring sufficiently, tetrakistriphenyl-phosphinopalladium (2.2 g, 1.9 mmol) was added. After the reaction for 3 hours, after cooling to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again put in chloroform 20 times 647 mL, dissolved, 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 recrystallized from chloroform and ethyl acetate to prepare a yellow solid compound 1-1-d (22.3 g, 69%, MS: [M+H] + = 505.6).

Step 5) Synthesis of compound 1-1

In a nitrogen atmosphere, 1-1-d (15 g, 29.7 mmol) and 9H-carbazole (5 g, 29.7 mmol) were added to 300 ml of dimethylformamide, stirred and refluxed. After that, potassium carboenite (12.3 g, 89.2 mmol) was added, followed by heating and stirring. After the reaction for 3 hours, the resulting solid was filtered after cooling to room temperature. The solid was dissolved in 30 times 584 mL of 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 through a silica column using chloroform and ethyl acetate to prepare a yellow solid compound 1-1 (10.3 g, 53%, MS: [M+H] + = 655.7).

Synthesis Example 2: Synthesis of compound 1-2

In Synthesis Example 1, 2-chloro-4-(dibenzo[b,d]furan-3-yl)-6-phenyl-1,3,5-triazine and 9H-carbazole were each 9-(4- By changing to chloro-6-phenyl-1,3,5-triazin-2-yl)-9H-carbazole and 9H-carbazole-1,2,3,4,5,6,7,8-d8 Except for the use, Compound 1-2 (MS: [M+H] ⁺ = 662.3)) was prepared in the same manner as that of Compound 1-1.

Synthesis Example 3: Synthesis of compound 1-3

In Synthesis Example 1, 2-bromo-5-chlorophenol, 2-chloro-4-(dibenzo[b,d]furan-3-yl)-6-phenyl-1,3,5-triazine and 9H -Except for using carbazole by changing it to 2-bromo-6-chlorophenol, 2-chloro-4,6-diphenyl-1,3,5-triazine and 4-phenyl-9H-carbazole , Compound 1-3 (MS[M+H] ⁺ = 641.2) was prepared by the same preparation method as that of compound 1-1.

Synthesis Example 4: Synthesis of compound 1-4

In Synthesis Example 1, (2,6-difluorophenyl) boronic acid, 2-chloro-4- (dibenzo [b, d] furan-3-yl) -6-phenyl-1,3,5-tri (2,5-difluorophenyl)boronic acid, 2-chloro-4,6-diphenyl-1,3,5-triazine and 9H-carbazole-1,2; Compound 1-4 (MS[M+H] ⁺ = 573.2) was prepared in the same manner as in the preparation method of compound 1-1, except that it was changed to 3,4,5,6,7,8-d8. prepared.

Synthesis Example 5: Synthesis of compound 1-5

In Synthesis Example 1, 2-bromo-5-chlorophenol, (2,6-difluorophenyl)boronic acid, and 9H-carbazole were mixed with 2-bromo-3-chlorophenol, (2,5-di Fluoro) boronic acid and 9H-carbazole-1,2,3,4,5,6,7,8-d8, except that the compound was used in the same manner as in the preparation method of Compound 1-1 Prepared 1-5 (MS[M+H] ⁺ = 663.2).

Synthesis Example 6: Synthesis of compound 1-6

In Synthesis Example 1, 2-bromo-5-chlorophenol, (2,6-difluorophenyl)boronic acid, 2-chloro-4-(dibenzo[b,d]furan-3-yl)-6 -Phenyl-1,3,5-triazine and 9H-carbazole, respectively, 2-bromo-3-chlorophenol, (2,4-difluorophenyl)boronic acid, 2-chloro-4,6-di Except for changing to phenyl-1,3,5-triazine and 4-(phenyl-d5)-9H-carbazole, Compound 1-6 (MS [M+H] ⁺ = 646.2).

Synthesis Example 7: Synthesis of compound 1-7

In Synthesis Example 1, 2-bromo-5-chlorophenol, (2,6-difluorophenyl)boronic acid, 2-chloro-4-(dibenzo[b,d]furan-3-yl)-6 -Phenyl-1,3,5-triazine and 9H-carbazole, respectively, 2-bromo-3-chloro-6-fluorophenol, (2-fluorophenyl)boronic acid, 2-chloro-4,6 -Diphenyl-1,3,5-triazine and 4-(phenyl-d5)-9H-carbazole were used in the same manner as in the preparation method of compound 1-1, except that compound 1-7 was used. (MS[M+H] ⁺ = 646.2) was prepared.

Synthesis Example 8: Synthesis of compound 1-8

In Synthesis Example 1, (2,6-difluorophenyl) boronic acid, 2-chloro-4- (dibenzo [b, d] furan-3-yl) -6-phenyl-1,3,5-tri Changing azine and 9H-carbazole to (2,4-difluorophenyl)boronic acid, 2-chloro-4,6-diphenyl-1,3,5-triazine and 3-phenyl-9H-carbazole Compound 1-8 (MS[M+H] ⁺ = 641.2) was prepared by the same preparation method as the preparation method of compound 1-1 except that it was used.

Synthesis Example 9: Synthesis of compounds 1-9

In Synthesis Example 1, (2,6-difluorophenyl) boronic acid, 2-chloro-4- (dibenzo [b, d] furan-3-yl) -6-phenyl-1,3,5-tri Azine and 9H-carbazole (2,4-difluorophenyl) boronic acid, 2-chloro-4- (dibenzo [b, d] thiophen-4-yl) -6-phenyl-1,3, Compound 1-9 (MS[M+H] ⁺ = 747.2) was prepared in the same manner as in the preparation method of compound 1-1, except that 5-triazine and 1-phenyl-9H-carbazole were used. prepared.

Synthesis Example 10: Synthesis of compound 1-10

In Synthesis Example 1, (2,6-difluorophenyl) boronic acid, 2-chloro-4- (dibenzo [b, d] furan-3-yl) -6-phenyl-1,3,5-tri Azine and 9H-carbazole (2,4-difluorophenyl) boronic acid, 2-chloro-4- (dibenzo [b, d] furan-4-yl) -6-phenyl-1,3,5 - Triazine and 3-(phenyl-d5)-9H-carbazole, except that it was used in the same manner as in the preparation method of compound 1-1, compound 1-10 (MS[M+H] ⁺ = 736.2) was prepared.

Synthesis example 11: Synthesis of compound 1-11

In Synthesis Example 1, (2,6-difluorophenyl) boronic acid, 2-chloro-4- (dibenzo [b, d] furan-3-yl) -6-phenyl-1,3,5-tri Azine and 9H-carbazole are each (2,3-difluorophenyl)boronic acid, 2-([1,1'-biphenyl]-4-yl)-4-chloro-6-phenyl-1,3 ,5-triazine and 9H-carbazole-1,2,3,4,5,6,7,8-d8, except that the compound was used in the same manner as in the preparation method of Compound 1-1 Prepared 1-11 (MS[M+H] ⁺ = 648.2).

Synthesis Example 12: Synthesis of compound 1-12

In Synthesis Example 1, (2,6-difluorophenyl) boronic acid, 2-chloro-4- (dibenzo [b, d] furan-3-yl) -6-phenyl-1,3,5-tri Azine and 9H-carbazole were each reacted with (2,3-difluorophenyl)boronic acid, 2-([1,1'-biphenyl]-3-yl)-4-chloro-6-phenyl-1,3 ,5-triazine and 9H-carbazole-1,2,3,4,5,6,7,8-d8, except that the compound was used in the same manner as in the preparation method of Compound 1-1 1-12 (MS[M+H] ⁺ = 648.2) were prepared.

Synthesis Example 13: Synthesis of compound 1-13

In Synthesis Example 1, 2-bromo-5-chlorophenol, (2,6-difluorophenyl)boronic acid, 2-chloro-4-(dibenzo[b,d]furan-3-yl)-6 -Phenyl-1,3,5-triazine and 9H-carbazole, respectively, 2-bromo-3-chlorophenol, (2,3-difluorophenyl)boronic acid, 2-chloro-4- (dibenzo [b,d]thiophen-4-yl)-6-phenyl-1,3,5-triazine and 9H-carbazole-1,2,3,4,5,6,7,8-d8 change Compound 1-13 (MS[M+H] ⁺ = 679.2) was prepared in the same manner as in the preparation method of compound 1-1, except that it was used.

Synthesis Example 14: Synthesis of compound 1-14

In Synthesis Example 1, 2-bromo-5-chlorophenol, (2,6-difluorophenyl)boronic acid, 2-chloro-4-(dibenzo[b,d]furan-3-yl)-6 -Phenyl-1,3,5-triazine and 9H-carbazole to 2-bromo-3-chlorophenol, (2,3-difluorophenyl)boronic acid, 2-chloro-4-phenyl-6- Except for using (phenyl-d5) -1,3,5-triazine and 4-phenyl-9H-carbazole, Compound 1-14 (MS [M+H] ⁺ = 646.2).

Synthesis Example 15: Synthesis of compound 1-15

In Synthesis Example 1, 2-bromo-5-chlorophenol, (2,6-difluorophenyl)boronic acid, 2-chloro-4-(dibenzo[b,d]furan-3-yl)-6 -Phenyl-1,3,5-triazine and 9H-carbazole, respectively, 2-bromo-3-chlorophenol, (2,3-difluorophenyl)boronic acid, 2-chloro-4- (dibenzo [b,d]furan-1-yl)-6-phenyl-1,3,5-triazine and 9H-carbazole-1,2,3,4,5,6,7,8-d8 Except for the use, Compound 1-15 (MS[M+H] ⁺ = 663.2) was prepared in the same manner as that of Compound 1-1.

Synthesis Example 16: Synthesis of compound 2-1

Step 1) Synthesis of compound 2-1-a

In a nitrogen atmosphere, 3-chloro-9H-carbazole (30 g, 148.8 mmol) and 2-bromodibenzo [b, d] furan (36.8 g, 148.8 mmol) were added to 600 ml of xylene, stirred and refluxed. Thereafter, sodium tert-butoxide (42.9 g, 446.3 mmol) was added, and after sufficient stirring, bis(tri-tertiary-butylphosphine)palladium (2.3 g, 4.5 mmol) was added. After the reaction for 4 hours, after cooling to room temperature, the organic layer was filtered to remove salt, and the filtered organic layer was distilled. This was again put into 547 mL of chloroform 10 times to dissolve, 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 through a silica column using chloroform and ethyl acetate to prepare a yellow solid compound 2-1-a (43.8 g, 80%, MS: [M+H] ⁺ = 368.8).

Step 2) Synthesis of compound 2-1-b

In a nitrogen atmosphere, 2-1-a (40 g, 108.7 mmol) and (9H-carbazol-3-yl)boronic acid (22.9 g, 108.7 mmol) were placed in 800 ml of Diox, stirred and refluxed. After that, potassium acetate (69.3 g, 326.2 mmol) was dissolved in 69 ml of water and thoroughly stirred, and then dibenzylideneacetone palladium (1.9 g, 3.3 mmol) and tricyclohexylphosphine (1.8 g, 6.5 mmol) were added. did. After the reaction for 6 hours, the resulting solid was filtered after cooling to room temperature. The solid was dissolved in 1627 mL of chloroform 30 times, 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 recrystallized from chloroform and ethyl acetate to prepare a yellow solid compound 2-1-b (38.5 g, 71%, MS: [M+H] ⁺ = 499.6).

Step 2) Synthesis of compound 2-1

In a nitrogen atmosphere, 2-1-b (30 g, 60.2 mmol) and bromobenzene (9.4 g, 60.2 mmol) were added to 600 ml of xylene, and the mixture was stirred and refluxed. Thereafter, sodium tert-butoxide (17.4 g, 180.5 mmol) was added, and after sufficient stirring, bis (tri-tertiary-butylphosphine) palladium (0.9 g, 1.8 mmol) was added. After the reaction for 3 hours, after cooling to room temperature, the organic layer was filtered to remove salt, and the filtered organic layer was distilled. This was again put into 346 mL of chloroform 10 times to dissolve, 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 through a silica column using chloroform and ethyl acetate to prepare a white solid compound 2-1 (27.7 g, 80%, MS: [M+H] ⁺ = 575.7).

Synthesis Example 17: Synthesis of compound 2-2

In Synthesis Example 16, 2-bromodibenzo [b, d] furan and bromobenzene were added to 4-bromodibenzo [b, d] furan and 2-bromonaphthalene-1,3,4,5,6, respectively, Compound 2-2 (MS[M+H] ⁺ = 632.2) was prepared in the same manner as in the preparation method of compound 2-1, except that it was changed to 7,8-d7 and used.

Synthesis Example 18: Synthesis of compound 2-3

In Synthesis Example 16, compound 2-3 (MS [M +H] ⁺ = 681.2).

Synthesis Example 19: Synthesis of compound 2-4

In Synthesis Example 16, compound 2-4 (MS [ M+H] ⁺ = 740.2).

Synthesis Example 20: Synthesis of compound 2-5

In Synthesis Example 16, 3-chloro-9H-carbazole, 2-bromodibenzo [b, d] furan, (9H-carbazol-3-yl) boronic acid and bromobenzene were each added to 3-chloro-9H- Carbazole-1,2,4,5,6,7,8-d7, 3-bromodibenzo [b, d] furan, (9H-carbazol-3-yl-1,2,4,5,6 ,7,8-d7) Compound 2-5 (MS [ M+H] ⁺ = 665.3).

Synthesis Example 21: Synthesis of compound 2-6

In Synthesis Example 16, 2-bromodibenzo [b, d] furan and bromobenzene were used by changing to 4-bromodibenzo [b, d] thiophene and 4-bromo-1,1'-biphenyl Except for that, compound 2-6 (MS[M+H] ⁺ = 667.2) was prepared in the same manner as that of compound 2-1.

Synthesis Example 22: Synthesis of compound 2-7

In Synthesis Example 16, by changing 2-bromodibenzo [b, d] furan and bromobenzene to 1-bromodibenzo [b, d] thiophene and 4 1-chloro-4- (phenyl-d5) naphthalene Except for the use, Compound 2-7 (MS[M+H] ⁺ = 722.2) was prepared in the same manner as that of Compound 2-1.

Synthesis Example 23: Synthesis of compound 2-8

In Synthesis Example 16, 2-bromodibenzo [b, d] furan was used by changing to 3-bromodibenzo [b, d] thiophene-1,2,4,6,7,8,9-d7 Except that, compound 2-8 (MS[M+H] ⁺ = 598.2) was prepared in the same manner as in the preparation method of compound 2-1.

[Example]

Example 1

A glass substrate coated with a thin film of 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, and after drying, it was 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 compound and the following PD compound were thermally vacuum deposited in a weight ratio of 95:5 to a thickness of 100 Å to form a hole injection layer, and then only the following HT-A compound had a thickness of 1150 Å was deposited to form a hole transport layer. On the hole transport layer, the following HT-B compound was thermally vacuum deposited to a thickness of 450 Å to form an electron blocking layer (electron blocking layer).

On the electron blocking layer, compound 1-1 and compound 2-1 prepared previously as a host compound and the following GD compound as a dopant compound were vacuum-deposited in a weight ratio of 85:15 to a thickness of 400 Å to form a light emitting layer. In this case, the weight ratio of the compound 1-1 to the compound 2-1 was 1:1.

On the light emitting layer, the following ET-A compound was vacuum-deposited to a thickness of 50 Å to form a hole blocking layer. On the hole blocking layer, the following ET-B compound and the following Liq compound were thermally vacuum deposited in a weight ratio of 2:1 to a thickness of 250 Å, and then LiF and magnesium were vacuum deposited to a thickness of 30 Å in a weight ratio of 1:1. Thus, an electron transport and injection layer was formed.

On the electron transport and injection layer, magnesium and silver were deposited to a thickness of 160 Å in a weight ratio of 1:4 to form a cathode, thereby manufacturing an organic light emitting diode.

In the above process, the deposition rate of the organic material was maintained at 0.4 ~ 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 silver and magnesium was maintained at 2 Å/sec, and the vacuum degree during deposition was 2 ×10 ^-7 to 5×10 ^-6 torr was maintained, an organic light emitting device was manufactured.

Examples 2 to 15

An organic light emitting diode was manufactured in the same manner as in Example 1, except that the compound shown in Table 1 was used instead of Compound 1 in Example 1.

At this time, the structure of the compound used in the Examples is summarized as follows.

.

Comparative Examples 1 to 9

An organic light emitting diode was manufactured in the same manner as in Example 1, except that the compound shown in Table 1 was used instead of Compound 1 in Example 1.

In this case, in Table 1 below, compounds H-2, C1 and C2 are as follows, respectively.

Experimental example

Voltage, efficiency, and lifetime (T95) were measured by applying a current to the organic light emitting diodes prepared in Examples and Comparative Examples, and the results are shown in Table 1 below. At this time, voltage and efficiency were measured by applying a current density of 10 mA/cm ² . In addition, T95 in Table 1 below means the time measured until the initial luminance is lowered to 95% at a current density of 20 mA/cm ² .

division light emitting compound Voltage (V)
(@10mA/cm ² ) Efficiency (cd/A)
(@10mA/cm ² ) luminous color T95(hr)
(@20mA/cm ² ) Example 1 compound 1-1, compound 2-1 3.02 69.8 green 80 Example 2 compound 1-2, compound 2-3 3.01 70.0 green 86 Example 3 compound 1-3, compound 2-3 3.05 72.1 green 79 Example 4 compound 1-4, compound 2-8 3.01 70.0 green 85 Example 5 compound 1-4, compound 2-4 3.00 72.3 green 82 Example 5 compound 1-5, compound 2-5 3.08 72.7 green 80 Example 6 compound 1-6, compound 2-3 3.01 70.2 green 81 Example 7 compound 1-7, compound 2-6 3.03 71.2 green 84 Example 8 compound 1-8, compound 2-6 2.99 72.5 green 80 Example 9 compound 1-9, compound 2-4 3.03 69.5 green 84 Example 10 compound 1-10, compound 2-4 3.02 73.9 green 82 Example 11 compound 1-11, compound 2-3 3.03 75.1 green 86 Example 12 compound 1-12, compound 2-5 3.05 75.6 green 90 Example 13 compound 1-13, compound 2-7 3.04 70.3 green 79 Example 14 compound 1-14, compound 2-6 3.06 74.6 green 86 Example 15 compound 1-15, compound 2-2 3.09 71.0 green 83 Comparative Example 1 compound 1-2 3.00 65.8 green 68 Comparative Example 2 compounds 1-8 3.03 65.5 green 65 Comparative Example 3 compound 1-12 3.00 62.0 green 69 Comparative Example 4 compound C1 3.05 60.1 green 62 Comparative Example 5 compound C2 3.25 58.7 green 59 Comparative Example 6 compound C1, compound H-2 3.12 67.5 green 72 Comparative Example 7 compound C1, compound 2-6 3.15 69.2 green 75 Comparative Example 8 compound C2, compound 2-1 3.20 68.2 green 75 Comparative Example 9 compound 1-8, compound H-2 3.25 65.8 green 78

As shown in Table 1, the organic light emitting devices of Examples using both the first compound and the second compound of the present invention as hosts, the organic light emitting devices of Comparative Examples 1 to 3 and the first compound using only the first compound and compared to the organic light emitting devices of Comparative Examples 4 and 5 in which neither the second compound was used, in terms of efficiency and lifespan, excellent characteristics were exhibited.

In addition, the organic light emitting device of the above example uses two kinds of hosts, but has higher efficiency and higher efficiency than the organic light emitting devices of Comparative Examples 6 to 9 in which a combination of other hosts is employed instead of the combination of the first compound and the second compound. It can be seen that an excellent lifespan is exhibited.

In general, considering that the luminous efficiency and lifespan characteristics of the organic light emitting device 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. means to indicate

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 transport and injection layer

Claims (17)

anode;
a negative electrode provided to face the positive electrode; and
a light emitting layer provided 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,
X is O or S;
X ₁ to X ₃ are each independently N or CH, provided that at least one of X ₁ to X ₃ is N,
Ar ₁ is unsubstituted or substituted with deuterium phenyl,
Ar ₂ is unsubstituted or substituted with one or more substituents selected from the group _consisting of deuterium, C _1-10 alkyl and C _6-20 aryl; containing one or two heteroatoms of N, O and S, unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium, C _1-10 alkyl and C _6-20 aryl; C _2-20 heteroaryl wherein at least one of the heteroatoms is N; or C _2-60 heteroaryl comprising heteroatoms O or S unsubstituted or substituted with deuterium;
R ₁ to R ₃ are each independently hydrogen; heavy hydrogen; or unsubstituted, or phenyl substituted with deuterium,
a+b is an integer from 0 to 6,
c is an integer from 0 to 8;
[Formula 2]

In Formula 2,
Y is O or S;
Ar ₃ is C _6-20 aryl; or C _2-20 heteroaryl comprising one or two heteroatoms of N, O and S;
wherein Ar ₃ is unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium, C _6-20 aryl and C _6-20 aryl substituted with deuterium,
R ₄ to R ₆ are each independently hydrogen; or deuterium,
d, e and f are each independently an integer of 0 to 7.
According to claim 1,
The first compound is represented by any one of the following formulas 1A' to 1E',
Organic light emitting device:
[Formula 1A']

[Formula 1B']

[Formula 1C']

[Formula 1D']

[Formula 1E']

In the formulas 1A' to 1E',
X, X ₁ to X ₃ , Ar ₁ , Ar ₂ , R ₁ to R ₃ , a+b and c are as defined in claim 1.
According to claim 1,
X is O;
organic light emitting device.
According to claim 1,
X ₁ to X ₃ are all N,
X ₁ and X ₂ are N and X ₃ is CH,
X ₁ and X ₃ are N and X ₂ is CH,
X ₁ is N, X ₂ and X ₃ are CH, or
X ₂ is N, and X ₁ and X ₃ are CH;
organic light emitting device.
According to claim 1,
Ar ₂ is unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium and C _6-20 aryl, phenyl, biphenylyl, naphthyl, phenanthryl, carbazolyl, benzoxazolyl, or benzothiazolyl; dibenzofuranyl unsubstituted or substituted with deuterium; or dibenzothiophenyl unsubstituted or substituted with deuterium;
organic light emitting device.
According to claim 1,
Ar ₁ is any one selected from the group consisting of

Ar ₂ is any one selected from the group consisting of
Organic light emitting device:

above,
m is an integer from 0 to 7.
According to claim 1,
R ₁ and R ₂ are hydrogen;
organic light emitting device.
delete According to claim 1,
said substituent

is any one of the substituents represented by the following formulas 3a to 3f,
Organic light emitting device:

In Formulas 3a to 3f,
p is an integer from 0 to 7.
According to claim 1,
a+b is 0, 1, 2, or 6,
c is 0, 1, 2, or 8;
organic light emitting device.
According to claim 1,
The first compound is any one selected from the group consisting of the following compounds,
Organic light emitting device:

.
According to claim 1,
Ar ₃ is phenyl, biphenylyl, naphthyl, phenanthrenyl, triphenylenyl, carbazolyl, dibenzofuranyl, dibenzothiophenyl, benzoxazolyl, or benzothiazolyl,
Here, Ar ₃ is unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium, C _6-20 aryl and C _6-20 aryl substituted with deuterium,
organic light emitting device.
delete According to claim 1,
d, e and f are each independently 0, 1, or 7;
organic light emitting device.
According to claim 1,
The second compound is represented by any one of the following formulas 2-1 to 2-4,
Organic light emitting device:
[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Formula 2-4]

In Formulas 2-1 to 2-4,
D means deuterium,
Y, Ar ₃ , R ₆ and f are as defined in claim 1.
According to claim 1,
The second compound is any one selected from the group consisting of the following compounds,
Organic light emitting device:

. delete

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