KR102352349B1 - Compound and organic light emitting device comprising the same - Google Patents

Abstract

The present specification relates to a compound of Formula 1 and an organic light emitting device including the same.

Description

Compound and organic light emitting device including same {COMPOUND AND ORGANIC LIGHT EMITTING DEVICE COMPRISING THE SAME}

This specification claims the benefit of the filing date of Korean Patent Application No. 10-2018-0158269 filed with the Korean Intellectual Property Office on December 10, 2018, the entire contents of which are incorporated herein by reference.

The present specification relates to a compound and an organic light emitting device including the same.

In general, the organic light emitting phenomenon refers to a phenomenon in which electric energy is converted into light energy using an organic material. An organic light emitting device using an organic light emitting phenomenon generally has a structure including an anode and a cathode and an organic material layer therebetween. Here, the organic material layer is often formed of a multi-layered structure composed of different materials in order to increase the efficiency and stability of the organic light-emitting device, 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. 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 these excitons are It lights up when it falls back to the ground state.

The development of new materials for the organic light emitting device as described above is continuously required.

US Patent Application Publication No. 2004-0251816

The present specification provides a compound and an organic light emitting device including the same.

The present invention provides a compound represented by the following formula (1).

[Formula 1]

In Formula 1,

X and Y are the same as or different from each other, each independently S or O,

R ₁ and R ₂ are the same as or different from each other, and each independently represent hydrogen, deuterium, a nitrile group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted an alkylaryl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, or adjacent substituents combine to form a ring,

R ₃ and R ₄ are the same as or different from each other, and each independently represent hydrogen or a nitrile group,

R ₅ and R ₆ are the same as or different from each other, and each independently represent hydrogen, a nitrile group, or a substituted or unsubstituted aryl group,

a, b and c are each an integer from 0 to 4,

d, e and f are each an integer from 0 to 3,

When a to f are plural, the substituents in parentheses are the same as or different from each other.

In addition, the first electrode; a second electrode provided to face the first electrode; and one or more organic material layers provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes the compound.

The compound according to an exemplary embodiment of the present specification may be used as a material of an organic material layer of an organic light emitting device, and by using it, it is possible to improve efficiency, low driving voltage and/or lifespan characteristics in an organic light emitting device.

1 illustrates an organic light emitting device according to an exemplary embodiment of the present specification.
2 illustrates an organic light emitting device according to another exemplary embodiment of the present specification.

Hereinafter, the present specification will be described in more detail.

The present specification provides a compound represented by Formula 1 above.

Examples of substituents in the present specification are described below, but are not limited thereto.

The term "substitution" means that a hydrogen atom bonded to a carbon atom of a compound is replaced with another substituent, and the position to be substituted is not limited as long as the position at which the hydrogen atom is substituted, that is, a position where the substituent is substitutable, is not limited, and when two or more are substituted , two or more substituents may be the same as or different from each other.

As used herein, the term "substituted or unsubstituted" refers to deuterium; nitrile group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted silyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted arylamine group; a substituted or unsubstituted aryl group; And it means that it is substituted with one or two or more substituents selected from the group consisting of a substituted or unsubstituted heterocyclic group, is substituted with a substituent to which two or more of the above-exemplified substituents are connected, or does not have any substituents. For example, the "substituent to which two or more substituents are connected" may be an aryl group substituted with an aryl group, an aryl group substituted with a heteroaryl group, a heterocyclic group substituted with an aryl group, an aryl group substituted with an alkyl group, and the like.

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 30. Specifically, it is preferably 1 to 20 carbon atoms. More specifically, it is preferable that it has 1-10 carbon atoms. Specific examples include a methyl group; ethyl group; Profile group; n-propyl group; isopropyl group; butyl group; n-butyl group; isobutyl group; tert-butyl group; sec-butyl group; 1-methylbutyl group; 1-ethylbutyl group; pentyl group; n-pentyl group; isopentyl group; neopentyl group; tert-pentyl group; hexyl group; n-hexyl group; 1-methylpentyl group; 2-methylpentyl group; 4-methyl-2-pentyl group; 3,3-dimethylbutyl group; 2-ethylbutyl group; heptyl group; n-heptyl group; 1-methylhexyl group; cyclopentylmethyl group; cyclohexylmethyl group; octyl group; n-octyl group; tert-octyl group; 1-methylheptyl group; 2-ethylhexyl group; 2-propylpentyl group; n-nonyl group; 2,2-dimethylheptyl group; 1-ethylpropyl group; 1,1-dimethylpropyl group; isohexyl group; 2-methylpentyl group; 4-methylhexyl group; 5-methylhexyl 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 30 carbon atoms, and more preferably has 3 to 20 carbon atoms. Specifically, a cyclopropyl group; cyclobutyl group; cyclopentyl group; 3-methylcyclopentyl group; 2,3-dimethylcyclopentyl group; cyclohexyl group; 3-methylcyclohexyl group; 4-methylcyclohexyl group; 2,3-dimethylcyclohexyl group; 3,4,5-trimethylcyclohexyl group; 4-tert-butylcyclohexyl group; cycloheptyl group; There is a cyclooctyl group, and the like, but is not limited thereto.

In the present specification, the alkoxy group may be a straight chain, branched chain or cyclic chain. Although carbon number of an alkoxy group is not specifically limited, It is preferable that it is C1-C30. Specifically, it is preferably 1 to 20 carbon atoms. More specifically, it is preferable that it has 1 to 10 carbon atoms. Specifically, a methoxy group; ethoxy group; n-propoxy group; isopropoxy group; i-propyloxy group; n-butoxy group; isobutoxy group; tert-butoxy group; sec-butoxy group; n-pentyloxy group; neopentyloxy group; isopentyloxy group; n-hexyloxy group; 3,3-dimethylbutyloxy group; 2-ethylbutyloxy group; n-octyloxy group; n-nonyloxy group; n-decyloxy group; benzyloxy group; It may be a p-methylbenzyloxy group, but is not limited thereto.

In the present specification, the amine group is -NH ₂ ; an alkylamine group; N-alkylarylamine group; arylamine group; N-aryl heteroarylamine group; It may be selected from the group consisting of an N-alkylheteroarylamine group and a heteroarylamine group, and the number of carbon atoms is not particularly limited, but is preferably 1 to 30. Specific examples of the amine group include a methylamine group; dimethylamine group; ethylamine group; diethylamine group; phenylamine group; naphthylamine group; biphenylamine group; anthracenylamine group; 9-methylanthracenylamine group; diphenylamine group; N-phenylnaphthylamine group; ditolylamine group; N-phenyltolylamine group; triphenylamine group; N-phenylbiphenylamine group; N-phenylnaphthylamine group; N-biphenylnaphthylamine group; N-naphthylfluorenylamine group; N-phenylphenanthrenylamine group; N-biphenylphenanthrenylamine group; N-phenylfluorenylamine group; N-phenylterphenylamine group; N-phenanthrenylfluorenylamine group; N-biphenylfluorenylamine group and the like, but is not limited thereto.

In the present specification, the silyl group may be represented by the formula of -SiRaRbRc, wherein Ra, Rb and Rc are the same as or different from each other, and each independently hydrogen; a substituted or unsubstituted alkyl group; Or it may be a substituted or unsubstituted aryl group. The silyl group is specifically a trimethylsilyl group; triethylsilyl group; t-butyldimethylsilyl group; vinyl dimethyl silyl group; propyldimethylsilyl group; triphenylsilyl group; diphenylsilyl group; There is a phenylsilyl group, but is not limited thereto.

In the present specification, the aryl group is not particularly limited, but preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms. The aryl group may be monocyclic or polycyclic. When the aryl group is a monocyclic aryl group, the number of carbon atoms is not particularly limited, but preferably 6 to 30 carbon atoms. More specifically, it is preferable that it has 6 to 20 carbon atoms. Specifically, the monocyclic aryl group includes a phenyl group; biphenyl group; It may be a terphenyl group, and the like, but is not limited thereto. When the aryl group is a polycyclic aryl group, the number of carbon atoms is not particularly limited. It is preferable that it has 10 to 30 carbon atoms, and more specifically, it is preferable that it has 10 to 20 carbon atoms. Specifically, the polycyclic aryl group includes a naphthyl group; anthracenyl group; phenanthryl group; triphenyl group; pyrenyl group; phenalenyl group; perylenyl group; chrysenyl group; It may be a fluorenyl group, but is not limited thereto.

As used herein, "adjacent" group means a substituent substituted on an atom directly connected to the atom in which the substituent is substituted, a substituent sterically closest to the substituent, or another substituent substituted on the atom in which the substituent is substituted. can For example, two substituents substituted at an ortho position in a benzene ring and two substituents substituted at the same carbon in an aliphatic ring may be interpreted as "adjacent" groups.

In the present specification, examples of the arylamine group include a substituted or unsubstituted monoarylamine group, a substituted or unsubstituted diarylamine group, or a substituted or unsubstituted triarylamine group. The aryl group in the arylamine group may be a monocyclic aryl group or a polycyclic aryl group. The arylamine group including two or more aryl groups may include a monocyclic aryl group, a polycyclic aryl group, or a monocyclic aryl group and a polycyclic aryl group at the same time. For example, the aryl group in the arylamine group may be selected from the examples of the aryl group described above.

In the present specification, the heteroaryl group includes one or more atoms other than carbon, that is, heteroatoms, and specifically, the heteroatoms may include one or more atoms selected from the group consisting of O, N, Se and S. The number of carbon atoms is not particularly limited, but preferably has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and the heteroaryl group may be monocyclic or polycyclic. Examples of the heteroaryl group include a thiophene group; furanyl group; pyrrole group; imidazolyl group; thiazolyl group; oxazolyl group; oxadiazolyl group; pyridyl group; bipyridyl group; pyrimidyl group; triazinyl group; triazolyl group; acrydyl group; pyridazinyl group; pyrazinyl group; quinolinyl group; quinazolinyl group; quinoxalinyl group; phthalazinyl group; pyrido pyrimidyl group; pyrido pyrazinyl group; pyrazino pyrazinyl group; isoquinolinyl group; indolyl group; carbazolyl group; benzoxazolyl group; benzimidazolyl group; benzothiazolyl group; benzocarbazolyl group; benzothiophene group; dibenzothiophene group; benzofuranyl group; a phenanthroline group; isoxazolyl group; thiadiazolyl group; There is a phenothiazinyl group and a dibenzofuranyl group, but is not limited thereto.

In an exemplary embodiment of the present specification, Chemical Formula 1 is represented by Chemical Formula 2 below.

[Formula 2]

In Formula 2, X, Y, R ₁ to R ₆ , a to d and f are as defined in Formula 1 above.

In an exemplary embodiment of the present specification, Chemical Formula 1 is represented by any one of Chemical Formulas 1-1 and 1-2 below.

[Formula 1-1]

[Formula 1-2]

In Formulas 1-1 and 1-2, X, Y, R ₁ to R ₆ and a to f are as defined in Formula 1 above.

In the exemplary embodiment of the present specification, Chemical Formula 1 is represented by any one of Chemical Formulas 2-1 and 2-2 below.

[Formula 2-1]

[Formula 2-2]

In Formulas 2-1 and 2-2, X, Y, R ₁ to R ₆ , a to d and f are as defined in Formula 1 above.

In an exemplary embodiment of the present specification, Chemical Formula 1 is represented by any one of the following Chemical Formulas 1-3 to 1-10.

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Formula 1-6]

[Formula 1-7]

[Formula 1-8]

[Formula 1-9]

[Formula 1-10]

In Formulas 1-3 to 1-10, X, Y, R ₁ to R _6, and a to f are as defined in Formula 1 above.

In an exemplary embodiment of the present specification, X and Y are O.

In the exemplary embodiment of the present specification, X and Y are S.

In an exemplary embodiment of the present specification, X is O, and Y is S.

In an exemplary embodiment of the present specification, X is S, and Y is O.

In an exemplary embodiment of the present specification, R ₁ and R ₂ are the same as or different from each other, and each independently represents hydrogen, a nitrile group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group.

In an exemplary embodiment of the present specification, R ₁ and R ₂ are the same as or different from each other, and each independently represents hydrogen, a nitrile group, an alkyl group, or an aryl group.

In an exemplary embodiment of the present specification, R ₁ and R ₂ are the same as or different from each other, and each independently hydrogen, a nitrile group, a substituted or unsubstituted C 1 to C 10 alkyl group, or a substituted or unsubstituted C 6 to 30 aryl groups.

In an exemplary embodiment of the present specification, R ₁ and R ₂ are the same as or different from each other, and each independently represent hydrogen, a nitrile group, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 30 carbon atoms.

In an exemplary embodiment of the present specification, R ₁ and R ₂ are the same as or different from each other, and each independently hydrogen, a nitrile group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a terbutyl group, a pentyl group , a hexyl group, a phenyl group, a biphenyl group, a terphenyl group, a quarterphenyl group, an anthracenyl group, a phenanthrenyl group, a naphthyl group, a pyrenyl group, a triphenylenyl group, or a fluorenyl group.

In an exemplary embodiment of the present specification, R ₁ and R ₂ are the same as or different from each other, and each independently represents hydrogen, a nitrile group, a methyl group, or a phenyl group.

In an exemplary embodiment of the present specification, R ₃ and R ₄ are the same as or different from each other, and each independently represent hydrogen or a nitrile group.

In an exemplary embodiment of the present specification, R ₃ and R ₄ are hydrogen.

In an exemplary embodiment of the present specification, R ₅ and R ₆ are the same as or different from each other, and each independently represent hydrogen, a nitrile group, or an aryl group having 6 to 30 carbon atoms.

In an exemplary embodiment of the present specification, R ₅ and R ₆ are the same as or different from each other, and each independently hydrogen, nitrile group, phenyl group, biphenyl group, naphthyl group, terphenyl group, quaterphenyl group, pyrenyl group, tri a phenylenyl group, an anthracenyl group, a phenanthrenyl group, or a fluorenyl group.

In an exemplary embodiment of the present specification, R ₅ and R ₆ are the same as or different from each other, and are each independently hydrogen, a nitrile group, or a phenyl group.

In the exemplary embodiment of the present specification, R ₅ is hydrogen, a nitrile group, or a phenyl group, and R ₆ is hydrogen.

In an exemplary embodiment of the present specification, Formula 1 is any one selected from the following compounds.

.

.

In the present specification, when a part "includes" a certain component, this means that other components may be further included rather than excluding other components unless otherwise stated.

In this specification, when a member is said to be located "on" another member, this includes not only a case in which a member is in contact with another member but also a case in which another member exists between the two members.

The organic light emitting device of the present invention also includes a first electrode; a second electrode provided to face the first electrode; and one or two or more organic material layers provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes the compound.

The structure of the organic light emitting device of the present invention may have the structure shown in FIGS. 1 and 2 , but is not limited thereto.

1 illustrates a structure of an organic light emitting device in which a first electrode 2 , an organic material layer 3 , and a second electrode 4 are sequentially stacked on a substrate 1 .

1 illustrates an organic light emitting device, but is not limited thereto.

2 shows the structure of an organic light emitting device in which a first electrode 2 , a first organic material layer 5 , a light emitting layer 6 , a second organic material layer 7 , and a second electrode 4 are sequentially stacked on a substrate 1 . is exemplified.

2 illustrates an organic light emitting device, and according to the first electrode and the second electrode, the first organic material layer and the second organic material layer may be a hole transport region and an electron transport region, respectively. In this case, the hole transport region means an organic material layer between the anode and the light emitting layer, for example, it includes at least one of a hole injection layer, a hole transport layer, and an electron blocking layer, and the electron transport region means an organic material layer between the cathode and the light emitting layer, For example, it includes at least one of an electron injection layer, an electron transport layer, and a hole blocking layer.

The organic light emitting device may have, for example, a stacked structure as follows, but is not limited thereto.

(1) anode / hole transport layer / light emitting layer / electron transport layer / cathode

(2) anode / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode

(3) anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / cathode

(4) anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode

(5) anode / hole transport layer / electron blocking layer / light emitting layer / electron transport layer / cathode

(6) anode / hole transport layer / electron blocking layer / light emitting layer / electron transport layer / electron injection layer / cathode

(7) anode / hole injection layer / hole transport layer / electron blocking layer / light emitting layer / electron transport layer / cathode

(8) anode / hole injection layer / hole transport layer / electron blocking layer / light emitting layer / electron transport layer / electron injection layer / cathode

(9) anode / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / cathode

(10) anode / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / electron injection layer / cathode

(11) anode / hole injection layer / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / cathode

(12) anode / hole injection layer / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / electron injection layer / cathode

(13) anode / hole injection layer / hole transport layer / electron blocking layer / light emitting layer / hole blocking layer / electron transport layer / electron injection layer / cathode

(14) anode / hole injection layer / hole transport layer / electron blocking layer / light emitting layer / hole blocking layer / electron transport layer / electron injection layer / cathode / capping layer

In an exemplary embodiment of the present invention, the organic material layer includes an emission layer, and the emission layer includes the compound of Formula 1 above.

In an exemplary embodiment of the present application, the light emitting layer includes the compound as a host.

In an exemplary embodiment of the present application, the light emitting layer includes the compound as a phosphorescent host.

In an exemplary embodiment of the present application, the light emitting layer includes a host and a dopant in a mass ratio of 99:1 to 1:99.

In an exemplary embodiment of the present application, the light emitting layer includes a host and a dopant in a mass ratio of 99:1 to 10:90.

In an exemplary embodiment of the present application, the light emitting layer includes a host and a dopant in a mass ratio of 99:1 to 50:50.

In another exemplary embodiment, the light emitting layer including the compound represented by Formula 1 may include the compound represented by Formula 1 as a host and a thermally activated delayed fluorescence compound as a dopant.

In the present specification, thermally activated delayed fluorescence compound (TADF, Thermally Activated Delayed Fluorescence) refers _{to a reverse energy transfer from the lowest triplet excitation state (T 1} ) to the lowest singlet excitation state (S ₁ ) by thermal activation, resulting in fluorescence It means a compound that exhibits a phenomenon leading to light emission.

In the present specification, delayed fluorescence refers to fluorescence that emits light through reverse-intersystem crossing of triplet excitons with singlet excitons.

In the present specification, the lowest excited triplet state (T ₁ ) is the energy of the triplet state having the lowest energy.

In the present specification, the triplet state means a state in which the sum of quantum numbers of spin angular momentum of all electrons is 1.

In the present specification, the lowest excited singlet state (S ₁ ) is the energy of the singlet state having the lowest energy.

In the present specification, the singlet state means a state in which the sum of quantum numbers of spin angular momentum of all electrons is 0.

In the present specification, the energies of the lowest excited triplet state (T ₁ ) and the lowest excited singlet state (S ₁ ) are determined by quantum chemical calculations.

The photoluminescence spectrum in the solid state (energy level in the lowest excited singlet state) and the photoluminescence spectrum in the low temperature state (the energy level in the lowest excitation triplet state) are measured, and the photoluminescence spectrum in the solid state is obtained from Perkin Elmer. It was measured using LS-55, the emission spectrum at an excitation wavelength of 370 nm was 400 nm to 660 nm, HPLC grade THF was used as a solvent, and the content of the compound was 1×10 ^-6 M. The photoluminescence spectrum in a low-temperature state was measured using LS-55 of Perkin Elmer, and the emission spectrum at an excitation wavelength of 445 nm was 400 nm to 700 nm. HPLC grade THF was used as a solvent, and it was measured under liquid nitrogen.

In the present specification, the difference (ΔE _st ) between the lowest triplet excited state (T ₁ ) and the lowest singlet excited state (S ₁ ) of the thermally activated delayed fluorescent compound is preferably greater than 0 eV and 0.2 eV or less.

In the present specification, when the difference (ΔE _{st ) between the lowest triplet excited state (T 1} ) and the lowest singlet excited state (S ₁ ) is small, preferably 0.2 eV or less, the singlet exciton emits light as it is. (ie, fluorescence), and a triplet exciton performs reverse-intersystem crossing with a singlet exciton to emit light (ie, delayed fluorescence). Accordingly, since the delayed fluorescence mechanism is added to the light emission by the fluorescence mechanism, it may be possible to increase the internal quantum efficiency to 100%.

When the difference (ΔE _st ) between the lowest excited triplet state (T ₁ ) and the lowest singlet excited state (S ₁ ) is greater than 0.2 eV, it is relatively difficult to cause inverse intersystem transition, so the occurrence of natural fluorescence is less. can get

_{In the present specification, the difference between the energy (Eg S} ) of the singlet state of the thermally activated delayed fluorescent compound and the energy _{at 77K} (Eg 77K ) may be expressed by the following formula.

ΔST= Eg _S - Eg _77K <0.3 eV

In the above formula, Eg _S and Eg _77K are values measurable through the energy level measurement method of the singlet state and triplet state, respectively, described above. fluorescence occurs.

In the present specification, the mixture of the compound represented by Formula 1 and the thermally activated delayed fluorescent compound is represented by │HOMO(Host)│>│HOMO(TADF)│, in order to prevent the formation of an exciplex of the emission layer, It is preferable that S ₁ (Host)>2.8eV and HOMO(Host)≥5.8eV.

The exciplex of the light emitting layer refers to a complex formed by bonding molecules in an excited state and a ground state between two different molecules.

In an exemplary embodiment of the present specification, when the compound represented by Formula 1 and the thermally activated delayed fluorescence compound are used together, the content of the thermally activated delayed fluorescence compound may be 1 to 60 parts by weight based on 100 parts by weight of the host.

In an exemplary embodiment of the present specification, when an additional host is used in addition to the compound of Formula 1 as a host, the content of the compound of Formula 1 may be 99 to 40 parts by weight based on 100 parts by weight of the host.

In one embodiment of the present specification, the thermally activated delayed fluorescence compound may be any one selected from the following compounds, but is not limited thereto.

.

.

In an exemplary embodiment of the present invention, the organic material layer includes a hole injection layer, a hole transport layer, or a hole injection and transport layer, and the hole injection layer, the hole transport layer, or the hole injection and transport layer may include the compound of Formula 1 can

In an exemplary embodiment of the present invention, the organic material layer includes an electron injection layer, an electron transport layer, or an electron injection and transport layer, and the electron injection layer, the electron transport layer, or the electron injection and transport layer may contain the compound of Formula 1 can

In an exemplary embodiment of the present invention, the organic material layer may include an electron blocking layer or a hole blocking layer, and the electron blocking layer or the hole blocking layer may include the compound of Formula 1 above.

For example, the organic light emitting device according to the present invention uses a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation, to form a metal or a conductive metal oxide or an alloy thereof on a substrate. to form an anode, an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an organic material layer including the compound of Formula 1 thereon, a material that can be used as a cathode is deposited thereon It can be manufactured by 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.

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 that can be used in the present invention 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); ZnO:Al or SnO ₂ : a combination of a metal such as Sb and an oxide; poly(3-methyl compound), poly[3,4-(ethylene-1,2-dioxy) compound] (PEDT), polypyrrole, and conductive polymers such as 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 negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead, or alloys thereof; and a multi-layered material such as LiF/Al or LiO ₂ /Al, but is not limited thereto.

The hole injection material is a material capable of well injecting holes from the anode at a low voltage, and it is preferable that the highest occupied molecular orbital (HOMO) of the hole injection material is between the work function of the anode material and the HOMO of the surrounding organic material layer. Specific examples of the hole injection material include metal porphyrine, oligothiophene, arylamine-based organic material, hexanitrile hexaazatriphenylene-based organic material, quinacridone-based organic material, and perylene-based organic material. of organic substances, anthraquinones, and conductive polymers based on polyaniline and polycompounds, but is not limited thereto.

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.

The light emitting material is a material capable of emitting light in the visible ray region by receiving and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, and a material having good quantum efficiency for fluorescence or phosphorescence is preferable. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq3); carbazole-based compounds; dimerized styryl compounds; BAlq; 10-hydroxybenzo quinoline-metal compounds; compounds of the benzoxazole, benzthiazole and benzimidazole series; Poly(p-phenylenevinylene) (PPV)-based polymers; spiro compounds; polyfluorene; Rubrene, and the like, but is not limited thereto.

When the organic light emitting device includes a plurality of organic material layers, the organic material layers may be formed of the same material or different materials.

The organic light emitting device of the present specification may be manufactured using materials and methods known in the art, except that at least one of the organic material layers is formed using the compound.

The present specification also provides a method of manufacturing an organic light emitting device formed using the compound.

Examples of the dopant material include an aromatic compound, a strylamine compound, a boron complex, a fluoranthene compound, and a metal complex. Specifically, the aromatic compound is a condensed aromatic ring derivative having a substituted or unsubstituted arylamino group, and includes pyrene, anthracene, chrysene, periflanthene, and the like, having an arylamino group. As the styrylamine compound, a substituted or unsubstituted A compound in which at least one arylvinyl group is substituted with an arylamine, 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, examples of the metal complex include, but are not limited to, an iridium complex and a platinum complex.

The electron transport layer is a layer that receives electrons from the electron injection layer and transports them to the light emitting layer. do. Specific examples include Al complex of 8-hydroxyquinoline; complexes comprising Alq3; 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.

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 with respect to the light emitting layer or the light emitting material, and hole injection of excitons generated in the light emitting layer A compound which prevents movement to a layer and is excellent in the ability to form a thin film is preferable. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, fluorenylidene methane, anthrone, etc., derivatives thereof, metals complex compounds and nitrogen-containing 5-membered ring derivatives, 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.

The electron blocking layer is a layer that blocks electrons from reaching the anode, and a material known in the art may be used as a material thereof.

The hole blocking layer is a layer that blocks the holes from reaching the cathode, and may be generally formed under the same conditions as the hole injection layer. Specifically, there are oxadiazole derivatives, triazole derivatives, phenanthroline derivatives, BCP, aluminum complex, and the like, but is not limited thereto.

The organic light emitting device according to the present specification may be a top emission type, a back emission type, or a double side emission type depending on the material used.

The organic light emitting device of the present invention may be manufactured by a conventional method and material for manufacturing an organic light emitting device, except for forming one or more organic material layers using the above-described compound.

In the following reaction scheme, various types of intermediates can be synthesized by those skilled in the art by appropriately selecting known starting materials for the type and number of substituents. As the reaction type and reaction conditions, those known in the art may be used.

<Scheme 1: Synthesis of Chemical Formula 1-1>

In Scheme 1, Ra and Rb are the same as the definitions of R1 and R2 in Formula 1, respectively,

Rc and Rd are as defined for R3 and R4 in Formula 1, respectively,

Rf and Rg are as defined for R5 and R6 in Formula 1, respectively,

l, m and n are each an integer from 0 to 4,

o, p and q are each an integer from 0 to 3,

When l to f are plural, the substituents in parentheses are the same as or different from each other.

go. Synthesis of Intermediate A

Under nitrogen, 0.4 mol of sm A, _{0.2 mol of iodine (I 2} ) and 0.2 mol of phenyl iodide diacetate (Ph-I(OAc) ₂ ) were mixed with 150 ml of acetic acid (AcOH) and 150 ml of acetic anhydride (Ac ₂ O). After adding three drops of sulfuric acid (H ₂ SO ₄ ), the mixture was stirred at room temperature for ten hours. After completion of the reaction, ethyl acetate was added to the mixed solution, washed with water, and then the layers were separated. Only the organic layer was received, anhydrous magnesium sulfate was added, stirred, filtered through a silica pad, and the solution was concentrated under reduced pressure. Thereafter, column purification was performed to obtain Intermediate A in 65% yield.

me. Synthesis of Intermediate B

Intermediate A 0.3mol, sm B 0.33mol and tetrakis(triphenylphosphine)palladium (Pd(PPh ₂ ) ₄ ) 2 mol% were added to 50 ml of tetrahydrofuran (THF) and potassium carbonate (K ₂ CO ₃ ) 0.6 mol was dissolved in 25 ml of water (H _{2 O) and mixed.}

After stirring at 80° C. for 12 hours, the reaction was terminated, cooled to room temperature, and the water and organic layers were separated. Only the organic layer was received, anhydrous magnesium sulfate was added, stirred, filtered through a silica pad, and the solution was concentrated under reduced pressure. Thereafter, column purification was performed to obtain Intermediate B in 70% yield.

All. Synthesis of Formula 1-1

Intermediate B 0.2 mol, sm C 0.2 mol, bis(tri-ter-butylphosphine)palladium(0)(Pd(t-Bu ₃ P) ₂ ) 1 mol% and sodium t-butoxide (NaOt-Bu) 0.24 mol was put into 70ml of toluene and stirred at 110°C for 12 hours. After completion of the reaction, the mixture was cooled to room temperature and filtered through a silica pad to remove impurities. After filtration, the solution was washed with water, only the organic layer was received, anhydrous magnesium sulfate was added, stirred, filtered through a silica pad, and the solution was concentrated under reduced pressure. Thereafter, column purification was performed to obtain the compound of Formula 1-1 in 63% yield.

<Scheme 2: Synthesis of Formula 1-2>

In Scheme 2, Ra and Rb are the same as the definitions of R1 and R2 in Formula 1, respectively,

Rc and Rd are as defined for R3 and R4 in Formula 1, respectively,

Rf and Rg are as defined for R5 and R6 in Formula 1, respectively,

l, m and n are each an integer from 0 to 4,

o, p and q are each an integer from 0 to 3,

When l to f are plural, the substituents in parentheses are the same as or different from each other.

go. Synthesis of Intermediate C

Under nitrogen, 0.4 mol of sm D and _{0.5 mol of bromine (Br 2} ) were placed in 150 ml of chloroform (Chloroform, CHCl ₃ ) and stirred at -40°C for 30 minutes. After completion of the reaction, an aqueous sodium bisulfate solution was added to the mixed solution, and then the layers were separated. Only the organic layer was received, anhydrous magnesium sulfate was added, stirred, filtered through a silica pad, and the solution was concentrated under reduced pressure. Thereafter, column purification was performed to obtain Intermediate C in 35% yield.

me. Synthesis of Intermediate D

Intermediate C 0.3mol, sm E 0.33mol and [1,1′-Bis(diphenylphosphino)ferrocene]dichloropalladium(II) ([1,1′-Bis(diphenylphosphino)ferrocene]dichloropalladium(II), Pd( dppf)Cl ₂ ) 2mol% was added to 50ml of tetrahydrofuran, and 0.6mol of potassium carbonate was dissolved in 25ml of water and mixed. After stirring at 80° C. for 12 hours, the reaction was terminated, cooled to room temperature, and the water and organic layers were separated. Only the organic layer was received, anhydrous magnesium sulfate was added, stirred, filtered through a silica pad, and the solution was concentrated under reduced pressure. Thereafter, column purification was performed to obtain Intermediate D in 70% yield.

All. Synthesis of Formula 1-2

Intermediate D 0.2mol, sm F 0.2mol, bis(tri-tert-butylphosphine)palladium(0) 1mol% and sodium t-butoxide 0.24mol were added to 70ml toluene and stirred at 110°C for 12 hours. After completion of the reaction, the mixture was cooled to room temperature and filtered through a silica pad to remove impurities. After filtration, the solution was washed with water, only the organic layer was received, anhydrous magnesium sulfate was added, stirred, filtered through a silica pad, and the solution was concentrated under reduced pressure. After column purification, the compound of Formula 1-2 was obtained in 63% yield.

By appropriately combining Scheme 1 or 2 of the present specification and the intermediates based on common technical knowledge, all of the compounds of Formula 1 described herein can be prepared.

A method of preparing the compound of Formula 1 and manufacturing an organic light emitting device using the same 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 1] Synthesis of compound 1

go. Synthesis of Intermediate 1-1

Under nitrogen, 10 g (40.65 mmol) of 4-bromodibenzofuran, 5.1 g (20.32 mmol) of iodine, and 6.6 g (20.32 mmol) of phenyl iodide diacetate were placed in a mixed solution of 150 ml of acetic acid and 150 ml of acetic anhydride, and sulfuric acid ( sulfuric acid) was added, followed by stirring at room temperature for ten hours. After completion of the reaction, ethyl acetate was added to the mixed solution, washed with water, and then the layers were separated. Only the organic layer was received, anhydrous magnesium sulfate was added thereto, stirred, filtered through a silica pad, and the solution was concentrated under reduced pressure. Thereafter, column purification was performed to obtain Intermediate 1-1 in 65% yield.

me. Synthesis of Intermediate 1-2

Intermediate 1-1 9.8g (26.35mmol), dibenzo[b,d]furan-4-yl boronic acid 6.15g (28.99mmol) and tetrakis(triphenylphosphine)palladium 2mol% were put in 80ml of tetrahydrofuran 7.3 g (52.70 mmol) of potassium carbonate was dissolved in 40 ml of water and mixed. After stirring at 80° C. for 12 hours, the reaction was terminated, cooled to room temperature, and the water and organic layers were separated. Only the organic layer was received, anhydrous magnesium sulfate was added, stirred, filtered through a silica pad, and the solution was concentrated under reduced pressure. Thereafter, column purification was performed to obtain Intermediate 1-2 in a yield of 60% (6.5 g).

All. Synthesis of compound 1

Intermediate 1-2 6.5g (15.78mmol), 9H-carbazole 2.6g (15.78mmol), bis(tri-tert-butylphosphine)palladium(0)1mol% and sodium t-butoxide 1.8g (18.94mmol) was put into 50ml toluene and stirred at 110°C for 12 hours. After completion of the reaction, the mixture was cooled to room temperature and filtered through a silica pad to remove impurities. After filtration, the solution was washed with water, only the organic layer was received, anhydrous magnesium sulfate was added, stirred, filtered through a silica pad, and the solution was concentrated under reduced pressure. Thereafter, column purification was performed to obtain compound 1 in 63% yield (4.96 g).

MS: [M+H]+= 500

[Synthesis Example 2] Synthesis of compound 2

Instead of 6.5 g (15.78 mmol) of Intermediate 1-2 and 2.6 g (15.78 mmol) of 9H-carbazole, 6 g (14.56 mmol) of Intermediate 1-2 and 3.5 g (14.56 mmol) of 2-phenyl-9H-carbazole were used. Except for the reaction and purification in the same manner as in the synthesis of Compound 1, Compound 2 was obtained in a yield of 61% (5.1 g).

MS: [M+H]+= 576

[Synthesis Example 3] Synthesis of compound 3

go. Synthesis of Intermediate 3-1

Except for using dibenzo[b,d]furan-1-ylboronic acid instead of dibenzo[b,d]furan-4-yl boronic acid, the reaction and purification were performed in the same manner as in the synthesis of Intermediate 1-2 above, followed by purification to Intermediate 3 -1 was obtained in a yield of 57% (6.2 g).

me. Synthesis of compound 3

The above compound except that 6.2 g (15.05 mmol) of Intermediate 3-1 and 2.5 g (15.05 mmol) of 9H-carbazole were used instead of 6.5 g (15.78 mmol) of Intermediate 1-2 and 2.6 g (15.78 mmol) of 9H-carbazole Reaction and purification were carried out in the same manner as in the synthesis of 1 to obtain compound 3 in a yield of 65% (4.9 g).

MS: [M+H]+= 500

[Synthesis Example 4] Synthesis of compound 4

go. Synthesis of Intermediate 4-1

Instead of 9.8 g (26.35 mmol) of Intermediate 1-1 and 6.15 g (28.99 mmol) of dibenzo[b,d]furan-4-yl boronic acid, 6g (16.14 mmol) of Intermediate 1-1 and dibenzo[b,d] The reaction and purification were performed in the same manner as in the synthesis of Intermediate 1-2, except that 3.96 g (17.75 mmol) of thiophen-2-yl boronic acid was used to obtain Intermediate 4-1 in 63% yield (4.4 g).

me. Synthesis of compound 4

The above compound except that 4.4 g (10.28 mmol) of Intermediate 4-1 and 1.7 g (10.28 mmol) of 9H-carbazole were used instead of 6.5 g (15.78 mmol) of Intermediate 1-2 and 2.6 g (15.78 mmol) of 9H-carbazole Reaction and purification were carried out in the same manner as in the synthesis of 1 to obtain compound 4 in a yield of 66% (5.3 g).

MS: [M+H]+= 516

[Synthesis Example 5] Synthesis of compound 5

go. Synthesis of Intermediate 5-1

Under nitrogen, 10 g (38.18 mmol) of 4-bromodibenzothiophene, 4.8 g (19.09 mmol) of iodine, and 6.2 g (19.09 mmol) of phenyl iodide diacetate were added to a mixed solution of 150 ml acetic acid and 150 ml acetic anhydride, and sulfuric acid After three drops of (sulfuric acid) were added, the mixture was stirred at room temperature for ten hours. After completion of the reaction, ethyl acetate was added to the mixed solution, washed with water, and then the layers were separated. Only the organic layer was received, anhydrous magnesium sulfate was added, stirred, filtered through a silica pad, and the solution was concentrated under reduced pressure. Thereafter, column purification was performed to obtain Intermediate 5-1 in 53% yield (7.8 g).

me. Synthesis of Intermediate 5-2

Intermediate 5-1 7.8g (18.22mmol), dibenzo[b,d]furan-4-yl boronic acid 4.3g (20.05mmol) and tetrakis(triphenylphosphine)palladium 2mol% were put in 60ml of tetrahydrofuran 5.0 g (36.44 mmol) of potassium carbonate was dissolved in 30 ml of water and mixed. After stirring at 80° C. for 12 hours, the reaction was terminated, cooled to room temperature, and the water and organic layers were separated. Only the organic layer was received, anhydrous magnesium sulfate was added, stirred, filtered through a silica pad, and the solution was concentrated under reduced pressure. Thereafter, column purification was performed to obtain Intermediate 5-2 in 61% yield (4.8 g).

All. Synthesis of compound 5

Intermediate 5-2 4.8g (11.22mmol), 9H-carbazole 1.9g (11.22mmol), bis(tri-tert-butylphosphine)palladium(0) 1mol% and sodium t-butoxide 1.3g (13.46mmol) was put into 30ml toluene and stirred at 110°C for 12 hours. After completion of the reaction, the mixture was cooled to room temperature and filtered through a silica pad to remove impurities. After filtration, the solution was washed with water, only the organic layer was received, anhydrous magnesium sulfate was added, stirred, filtered through a silica pad, and the solution was concentrated under reduced pressure. Thereafter, column purification was performed to obtain compound 5 in 58% yield (3.4 g).

MS: [M+H]+= 516

[Synthesis Example 6] Synthesis of compound 6

Instead of 4.8 g (11.22 mmol) of Intermediate 5-2 and 1.9 g (11.22 mmol) of 9H-carbazole, 8 g (18.69 mmol) of Intermediate 5-2 and 3.6 g (18.69 mmol) of 3,6-dimethyl-9H-carbazole were used. Except for the use, reaction and purification were performed in the same manner as in the synthesis of compound 5 to obtain compound 6 in a yield of 59% (5.9 g).

MS: [M+H]+= 544

[Synthesis Example 7] Synthesis of compound 7

go. Synthesis of Intermediate 7-1

Under nitrogen, 10 g (34.02 mmol) of 1-iodo dibenzofuran and 2.7 g (17.01 mmol) of bromine were placed in 140 ml of chloroform and stirred at -40°C for 30 minutes. After completion of the reaction, an aqueous sodium bisulfate solution was added to the solution, and then the layers were separated. Only the organic layer was received, anhydrous magnesium sulfate was added, stirred, filtered through a silica pad, and the solution was concentrated under reduced pressure. Thereafter, column purification was performed to obtain Intermediate 7-1 in 35% yield (4.4 g).

me. Synthesis of Intermediate 7-2

Intermediate 7-1 4.4g (11.83mmol), dibenzo[b,d]furan-4-yl boronic acid 2.8g (13.01mmol) and tetrakis(triphenylphosphine)palladium 2mol% were added to 30ml of tetrahydrofuran 3.27 g (23.66 mmol) of potassium carbonate was dissolved in 15 ml of water and mixed. After stirring at 80° C. for 12 hours, the reaction was terminated, cooled to room temperature, and the water and organic layers were separated. Only the organic layer was received, anhydrous magnesium sulfate was added, stirred, filtered through a silica pad, and the solution was concentrated under reduced pressure. Thereafter, column purification was performed to obtain Intermediate 7-2 in 60% yield (2.9 g).

All. Synthesis of compound 7

Intermediate 7-2 2.9 g (7.04 mmol), 9H-carbazole 1.2 g (7.04 mmol), bis (tri-tert-butylphosphine) palladium (0) 1 mol% and sodium t-butoxide 0.8 g (8.45 mmol) was put into 20ml toluene and stirred at 110°C for 12 hours. After completion of the reaction, the mixture was cooled to room temperature and filtered through a silica pad to remove impurities. After filtration, the solution was washed with water, only the organic layer was received, anhydrous magnesium sulfate was added, stirred, filtered through a silica pad, and the solution was concentrated under reduced pressure. Thereafter, column purification was performed to obtain compound 7 in 65% yield (2.3 g).

MS: [M+H]+= 500

[Synthesis Example 8] Synthesis of compound 8

go. Synthesis of Intermediate 8-1

Instead of 4.4 g (11.83 mmol) of Intermediate 7-1 and 2.8 g (13.01 mmol) of dibenzo [b,d] furan-4-yl boronic acid, 6 g (16.14 mmol) of Intermediate 7-1 and dibenzo [b, d] Except for using 3.7 g (17.75 mmol) of furan-1-yl boronic acid, the reaction and purification were performed in the same manner as in the synthesis of Intermediate 7-2 to obtain Intermediate 8-1 in a yield of 60% (3.9 g).

me. Synthesis of compound 8

The above compound except that 3.9 g (9.47 mmol) of Intermediate 8-1 and 1.6 g (9.47 mmol) of 9H-carbazole were used instead of 2.9 g (7.04 mmol) of Intermediate 7-2 and 1.2 g (7.04 mmol) of 9H-carbazole The reaction and purification were carried out in the same manner as in the synthesis of 7 to obtain compound 8 in a yield of 58% (2.7 g).

MS: [M+H]+= 500

[Synthesis Example 9] Synthesis of compound 9

Instead of 2.9 g (7.04 mmol) of Intermediate 7-2 and 1.2 g (7.04 mmol) of 9H-carbazole, 6.0 g (14.56 mmol) of Intermediate 7-2 and 2.8 g (14.56 mmol) of 9H-carbazole-3-carbonitrile were used. Except for the use, reaction and purification were performed in the same manner as in the synthesis of compound 7 to obtain compound 9 in a yield of 62% (4.7 g).

MS: [M+H]+= 525

[Synthesis Example 10] Synthesis of compound 10

go. Synthesis of Intermediate 10-1

1-iododibenzothiophene under nitrogen 10g (32.26mmol) and 2.7g (16.13mmol) of bromine were placed in 140ml chloroform and stirred at -40°C for 30 minutes. After completion of the reaction, an aqueous sodium bisulfate solution was added to the solution, and then the layers were separated. Only the organic layer was received, anhydrous magnesium sulfate was added, stirred, filtered through a silica pad, and the solution was concentrated under reduced pressure. Thereafter, column purification was performed to obtain Intermediate 10-1 in 31% yield (3.8 g).

me. Synthesis of Intermediate 10-2

Intermediate 10-1 3.8g (9.80mmol), dibenzo[b,d]furan-4-yl boronic acid 2.3g (10.78mmol) and tetrakis(triphenylphosphine)palladium 2mol% were added to 30ml of tetrahydrofuran 2.7 g (19.60 mmol) of potassium carbonate was dissolved in 15 ml of water and mixed. After stirring at 80° C. for 12 hours, the reaction was terminated, cooled to room temperature, and the water and organic layers were separated. Only the organic layer was received, anhydrous magnesium sulfate was added, stirred, filtered through a silica pad, and the solution was concentrated under reduced pressure. Thereafter, column purification was performed to obtain Intermediate 10-2 in 63% yield (2.6 g).

All. Synthesis of compound 10

Intermediate 10-2 2.6g (6.07mmol), 9H-carbazole 1.0g (6.07mmol), bis(tri-tert-butylphosphine)palladium(0)1mol% and sodium t-butoxide 0.7g (7.28mmol) was put into 20ml toluene and stirred at 110°C for 12 hours. After completion of the reaction, the mixture was cooled to room temperature and filtered through a silica pad to remove impurities. After filtration, the solution was washed with water, only the organic layer was received, added anhydrous magnesium sulfate, stirred, filtered through a silica pad, and the solution was concentrated under reduced pressure. Thereafter, column purification was performed to obtain compound 10 in 59% yield (1.8 g).

MS: [M+H]+= 516

[Synthesis Example 11] Synthesis of compound 11

go. Synthesis of Intermediate 11-1

Instead of 3.8 g (9.80 mmol) of Intermediate 10-1 and 2.3 g (10.78 mmol) of dibenzo [b,d] furan-4-yl boronic acid, 6 g (15.47 mmol) of Intermediate 10-1 and dibenzo [b, d] Except for using 3.6 g (17.02 mmol) of furan-1-yl boronic acid, the reaction and purification were performed in the same manner as in the synthesis of Intermediate 10-2 to obtain Intermediate 11-1 in a yield of 59% (3.8 g).

me. Synthesis of compound 11

The above compound except that 3.8 g (8.88 mmol) of Intermediate 11-1 and 1.5 g (8.88 mmol) of 9H-carbazole were used instead of 2.6 g (6.07 mmol) of Intermediate 10-2 and 1.0 g (6.07 mmol) of 9H-carbazole. The reaction and purification were carried out in the same manner as in the synthesis of 10 to obtain compound 11 in a yield of 64% (2.9 g).

MS: [M+H]+= 516

<Experimental Example 1-1>

A glass substrate coated with a thin film of ITO (ndium tin oxide) to a thickness of 1,000 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. Each layer of the organic light emitting device was deposited in the following order by evaporation from a heating boat under a vacuum of about 10 ^{-7 Torr.} At this time, the deposition rate of the organic material or inorganic material was set to 1 Å/s.

On the thus prepared ITO transparent electrode, m-MTDATA (60 nm) / TCTA (80 nm) / Host + 10 wt% Ir (ppy) ₃ (300 nm) / BCP (10 nm) / Alq3 (30 nm) / LiF (1 nm) / Al (200 nm) to construct an organic light emitting device, and the organic light emitting device was prepared using Compound 1 as the host.

The structures of m-MTDATA, TCTA, Ir(ppy) ₃ , BCP and Alq3 are as follows, respectively.

[Alq3]

<Experimental Example 1-2>

An organic light emitting diode was manufactured in the same manner as in Experimental Example 1-1, except that Compound 2 was used instead of Compound 1 in Experimental Example 1-1.

<Experimental Example 1-3>

An organic light emitting diode was manufactured in the same manner as in Experimental Example 1-1, except that Compound 3 was used instead of Compound 1 in Experimental Example 1-1.

<Experimental Example 1-4>

An organic light emitting diode was manufactured in the same manner as in Experimental Example 1-1, except that Compound 4 was used instead of Compound 1 in Experimental Example 1-1.

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<Experimental Example 1-7>

An organic light emitting diode was manufactured in the same manner as in Experimental Example 1-1, except that Compound 7 was used instead of Compound 1 in Experimental Example 1-1.

<Experimental Example 1-8>

An organic light emitting diode was manufactured in the same manner as in Experimental Example 1-1, except that Compound 8 was used instead of Compound 1 in Experimental Example 1-1.

<Experimental Example 1-9>

An organic light emitting diode was manufactured in the same manner as in Experimental Example 1-1, except that Compound 9 was used instead of Compound 1 in Experimental Example 1-1.

<Comparative Example 1-1>

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An organic light emitting diode was manufactured in the same manner as in Experimental Example 1-1, except that GH 1 was used instead of Compound 1 in Experimental Example 1-1.

<Comparative Example 1-2>

An organic light emitting diode was manufactured in the same manner as in Experimental Example 1-1, except that GH 2 was used instead of Compound 1 in Experimental Example 1-1.

<Comparative Example 1-3>

An organic light emitting diode was manufactured in the same manner as in Experimental Example 1-1, except that GH 3 was used instead of Compound 1 in Experimental Example 1-1.

<Comparative Example 1-4>

An organic light emitting diode was manufactured in the same manner as in Experimental Example 1-1, except that GH 4 was used instead of Compound 1 in Experimental Example 1-1.

When a current ^{of 10 mA/cm 2} was applied to the organic light emitting devices manufactured by Experimental Examples 1-1 to 1-4 and 1-7 to 1-9 and Comparative Examples 1-1 to 1-4, got the result

compound
(host) Voltage
(V@10mA/cm ² ) efficiency
(cd/A@10mA/cm ² ) EL peak
(nm) Experimental Example 1-1 compound 1 3.74 42.77 517 Experimental Example 1-2 compound 2 3.81 42.53 515 Experimental Example 1-3 compound 3 3.86 43.61 518 Experimental Example 1-4 compound 4 3.67 42.58 517 Experimental Example 1-7 compound 7 3.74 44.55 516 Experimental Example 1-8 compound 8 3.65 42.50 517 Experimental Example 1-9 compound 9 3.80 42.59 518 Comparative Example 1-1 GH 1 5.78 38.08 517 Comparative Example 1-2 GH 2 5.90 37.17 517 Comparative Example 1-3 GH 3 5.67 36.41 517 Comparative Example 1-4 GH 4 5.82 36.58 517

As a result of the experiment, the green organic light-emitting devices of Experimental Examples using the compounds according to the present invention as a host material for the light-emitting layer were more current than the green organic light-emitting devices of Comparative Examples 1-1 to 1-4 using a conventional green host (GH). and excellent performance in terms of driving voltage.

<Experimental Example 2-1>

An organic light-emitting device was fabricated in which Compound 1 was applied as a host of the light-emitting material layer. First, a glass substrate with an ITO (including a reflector) electrode having a thickness of 40 mm × 40 mm × 0.5 mm was ultrasonically cleaned with isopropyl alcohol, acetone, and DI water for 5 minutes, and then dried in an oven at 100°C. _{After cleaning the substrate, O 2} plasma treatment was performed for 2 minutes in a vacuum state and transferred to a deposition chamber to deposit other layers thereon. Each layer of the organic light emitting device was deposited in the following order by evaporation from a heating boat under a vacuum of about 10 ^{-7 Torr.} At this time, the deposition rate of the organic material or inorganic material was set to 1 Å/s.

On the ITO transparent electrode, through the above-described method, a hole injection layer (HIL; HAT-CN, 70 Å), a hole transport layer (HTL; NPB, 780 Å), an electron blocking layer (EBL; mCBP, 150 Å), a light emitting material layer (EML; compound 1 is used as a host and BDpyInCz is doped at 30 wt% with a delayed fluorescent material, 350 Å), a hole blocking layer (HBL; B3PYMPM; 100 Å), an electron transport layer (ETL: TPBi, 250 Å) and electrons An organic light-emitting device was manufactured in this order of an injection layer (EIL; LiF, 8 Å) and a cathode (Al; 1000 Å).

The structures of HAT-CN, NPB, mCBP, BDpyInCz, B3PYMPM and TPBi are as follows, respectively.

A capping layer was formed by the CPL and then encapsulated with glass. After deposition of these layers, they were transferred from the deposition chamber into a drying box for film formation and subsequently encapsulated using UV curing epoxy and moisture getter.

<Experimental Example 2-2>

An organic light emitting diode was manufactured in the same manner as in Experimental Example 2-1, except that Compound 2 was used instead of Compound 1 in Experimental Example 2-1.

<Experimental Example 2-3>

An organic light emitting diode was manufactured in the same manner as in Experimental Example 2-1, except that Compound 3 was used instead of Compound 1 in Experimental Example 2-1.

<Experimental Example 2-4>

An organic light emitting diode was manufactured in the same manner as in Experimental Example 2-1, except that Compound 4 was used instead of Compound 1 in Experimental Example 2-1.

<Experimental Example 2-7>

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An organic light emitting diode was manufactured in the same manner as in Experimental Example 2-1, except that Compound 7 was used instead of Compound 1 in Experimental Example 2-1.

<Experimental Example 2-8>

An organic light emitting diode was manufactured in the same manner as in Experimental Example 2-1, except that Compound 8 was used instead of Compound 1 in Experimental Example 2-1.

<Experimental Example 2-9>

An organic light emitting diode was manufactured in the same manner as in Experimental Example 2-1, except that Compound 9 was used instead of Compound 1 in Experimental Example 2-1.

<Comparative Example 2-1>

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An organic light emitting diode was manufactured in the same manner as in Experimental Example 2-1, except that GH 1 was used instead of Compound 1 in Experimental Example 2-1.

<Comparative Example 2-2>

An organic light emitting diode was manufactured in the same manner as in Experimental Example 2-1, except that GH 2 was used instead of Compound 1 in Experimental Example 2-1.

<Comparative Example 2-3>

An organic light emitting diode was manufactured in the same manner as in Experimental Example 2-1, except that GH 3 was used instead of Compound 1 in Experimental Example 2-1.

<Comparative Example 2-4>

An organic light emitting diode was manufactured in the same manner as in Experimental Example 2-1, except that GH 4 was used instead of Compound 1 in Experimental Example 2-1.

When a current of 6.3J was applied to the organic light emitting devices manufactured according to Experimental Examples 2-1 to 2-4, 2-7 to 2-9, and Comparative Examples 2-1 to 2-4, the results shown in Table 2 were obtained. .

compound
(host) Voltage
(V@6.3J) EQE
(%) CIE x CIE y Experimental Example 2-1 compound 1 4.14 20.0 0.341 0.586 Experimental Example 2-2 compound 2 4.21 19.1 0.367 0.580 Experimental Example 2-3 compound 3 4.28 19.4 0.372 0.584 Experimental Example 2-4 compound 4 4.14 18.6 0.364 0.584 Experimental Example 2-7 compound 7 4.14 19.6 0.373 0.573 Experimental Example 2-8 compound 8 4.06 18.8 0.371 0.571 Experimental Example 2-9 compound 9 4.22 19.9 0.388 0.588 Comparative Example 2-1 GH 1 6.42 16.2 0.381 0.581 Comparative Example 2-2 GH 2 6.52 16.1 0.388 0.588 Comparative Example 2-3 GH 3 7.10 15.9 0.371 0.571 Comparative Example 2-4 GH 4 6.81 16.2 0.363 0.563

When the organic compound synthesized according to the present invention is used as a host of the delayed fluorescent light emitting material layer, compared to the case of using GH 1 to GH 4 of Comparative Examples 2-1 to 2-4 as a host, the driving voltage is lowered and Efficiency (EQE) is improved. As a result, it was confirmed that by applying the organic compound of the present invention to the organic light emitting layer, the driving voltage of the light emitting diode can be lowered, the light emitting efficiency can be improved, and the color purity can be improved. Therefore, by using the organic light emitting device to which the organic compound of the present invention is applied, it can be utilized in a light emitting device such as an organic light emitting device display device and/or a lighting device with reduced power consumption and improved luminous efficiency and device lifespan.

1: Substrate
2: first electrode
3: organic layer
4: second electrode
5: light emitting layer

Claims (12)

A compound represented by any one of Formulas 1-1 and 1-2:
[Formula 1-1]

[Formula 1-2]

In Formulas 1-1 and 1-2,
X is O;
Y is S or O;
R ₁ and R ₂ are the same as or different from each other, and each independently represent hydrogen, deuterium, a nitrile group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted an alkylaryl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group,
R ₃ and R ₄ are the same as or different from each other, and each independently represent hydrogen or a nitrile group,
R ₅ and R ₆ are the same as or different from each other, and each independently represent hydrogen, a nitrile group, or a substituted or unsubstituted aryl group,
a, b and c are each an integer from 0 to 4,
d, e and f are each an integer from 0 to 3,
When a to f are plural, the substituents in parentheses are the same as or different from each other,
Here, "substituted or unsubstituted" means deuterium; nitrile group; an alkyl group; cycloalkyl group; silyl group; alkoxy group; arylamine group; aryl group; And it means that it is substituted with one or two or more substituents selected from the group consisting of a heterocyclic group, is substituted with a substituent to which two or more of the above exemplified substituents are connected, or does not have any substituents. delete The compound of claim 1, wherein R ₁ and R ₂ are the same as or different from each other, and each independently represent hydrogen, a nitrile group, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 30 carbon atoms. The compound of claim 1, wherein R ₅ and R ₆ are the same as or different from each other, and each independently represent hydrogen, a nitrile group, or an aryl group having 6 to 30 carbon atoms. The compound according to claim 1, wherein Formula 1 is any one selected from the following compounds:

. a first electrode; a second electrode provided to face the first electrode; and one or more organic material layers provided between the first electrode and the second electrode, wherein one or more of the organic material layers comprises the compound of any one of claims 1 and 3 to 5 Phosphorus organic light emitting device. The organic light emitting device of claim 6 , wherein the organic material layer includes an emission layer, and the emission layer includes a host and a dopant in a mass ratio of 99:1 to 50:50. The organic light-emitting device of claim 6 , wherein the organic material layer includes an emission layer, and the emission layer includes the compound as a host. 8. The method of claim 7,
The light emitting layer is an organic light emitting device comprising the compound as a phosphorescent host. 8. The method of claim 7,
The light emitting layer includes the compound as a host, and an organic light emitting device comprising a thermally activated delayed fluorescence compound as a dopant. The organic according to claim 10, wherein the dopant comprises a thermally activated delayed fluorescence compound having a gap (ΔE _{st ) between the lowest triplet excited state (T 1} ) and the lowest singlet excited state (S ₁ ) of 0.2 eV or less. light emitting element. The organic light emitting diode of claim 11 , wherein the thermally activated delayed fluorescence compound is represented by any one of the following structural formulas:

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