KR102294541B1 - Heterocyclic compound and organic light emitting device comprising the same - Google Patents

Abstract

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

Description

Heterocyclic compound and organic light emitting device comprising the same

The present specification relates to a heterocyclic 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, and may include, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like. In the structure of the organic light emitting device, when a voltage is applied between the two electrodes, holes are injected into the organic material layer from the anode and electrons from the cathode are injected into the organic material layer. When the injected holes and electrons meet, excitons are formed, and the excitons When it falls back to the ground state, it lights up.

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

US Patent Application Publication No. 2004-0251816

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

An exemplary embodiment of the present specification provides a heterocyclic compound represented by the following formula (1).

[Formula 1]

In Formula 1,

X1 is O or S;

R1 and R2 are the same as or different from each other, and each independently a substituted or unsubstituted alkyl group; Or a substituted or unsubstituted aryl group,

Ar1 is a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

R3 to R5 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

r3 to r5 are each an integer of 1 to 4,

When r3 is 2 or more, two or more of R3 are the same as or different from each other,

When r4 is 2 or more, two or more of R4 are the same as or different from each other,

When r5 is two or more, two or more of R5 are the same as or different from each other.

In addition, an exemplary embodiment of the present specification includes a first electrode; a second electrode provided to face the first electrode; and at least one organic material layer provided between the first electrode and the second electrode, wherein at least one layer of the organic material layer includes the compound represented by Formula 1 above. .

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

1 and 2 show an organic light emitting device according to an 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.

Formula 1 according to an exemplary embodiment of the present specification is a substituted fluorene-condensed core and a substituted benzofuropyrimidine, or a substituted fluorene-condensed indole-condensed core and a substituted benzothienopyrimidine. In the structure, since Ar1, R1 and R2 include the substituents, Chemical Formula 1 has a high glass transition temperature (Tg) and thermal stability. It works.

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; halogen group; cyano group; an alkyl group; cycloalkyl group; alkenyl group; alkoxy group; aryloxy group; aryl group; And it means that it is substituted with one or more substituents selected from the group consisting of a heteroaryl 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, "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, 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 30. Specific examples 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-dimethyl heptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, and the like.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 30 carbon atoms, and 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, etc., but are limited thereto it is not

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 30. 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 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, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, isopentyloxy, n -hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, benzyloxy, p-methylbenzyloxy, etc. may be It is not limited.

In the present specification, the aryl group is not particularly limited, but preferably has 6 to 30 carbon atoms, and 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. Specifically, the monocyclic aryl group may be a phenyl group, a biphenyl group, 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 is C10-30. Specifically, the polycyclic aryl group may be a naphthyl group, an anthracene group, a phenanthrene group, a triphenylene group, a pyrene group, a phenalene group, a perylene group, a chrysene group, a fluorene group, and the like, but is not limited thereto.

In the present specification, the fluorenyl group may be substituted, and adjacent groups may combine with each other to form a ring.

,

,

,

,

,

,

및

등이 있으나, 이에 한정되지 않는다.When the fluorenyl group is substituted,

,

,

,

,

,

,

and

and the like, 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, the heteroaryl group includes one or more atoms other than carbon and heteroatoms, and specifically, the heteroatoms may include one or more atoms selected from the group consisting of O, N, Se and S, and the like. The number of carbon atoms is not particularly limited, but preferably has 2 to 30 carbon atoms, and the heteroaryl group may be monocyclic or polycyclic. Examples of the heterocyclic group include a thiophene group, a furan group, a pyrrole group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a pyridine group, a bipyridine group, a pyrimidine group, a triazine group, a triazole group, an acridine group. , pyridazine group, pyrazine group, quinoline group, quinazoline group, quinoxaline group, phthalazine group, pyrido pyrimidine group, pyrido pyrazine group, pyrazino pyrazine group, isoquinoline group, indole group, carbazole group, benz Oxazole group, benzimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuran group, phenanthridine group, phenanthridine group, phenanthroline group, isoxazole group, thia There are a diazole group, a phenothiazine group, and a dibenzofuran group, but is not limited thereto.

In the present specification, the aryl group in the aryloxy group is the same as the example of the aryl group described above. Specifically, the aryloxy group includes a phenoxy group, p-tolyloxy group, m-tolyloxy group, 3,5-dimethyl-phenoxy group, 2,4,6-trimethylphenoxy group, p-tert-butylphenoxy group, 3- Biphenyloxy group, 4-biphenyloxy group, 1-naphthyloxy group, 2-naphthyloxy group, 4-methyl-1-naphthyloxy group, 5-methyl-2-naphthyloxy group, 1-anthryloxy group , 2-anthryloxy group, 9-anthryloxy group, 1-phenanthryloxy group, 3-phenanthryloxy group, 9-phenanthryloxy group, and the like, but is not limited thereto.

According to an exemplary embodiment of the present specification, in Formula 1, R3 to R5 are hydrogen.

According to an exemplary embodiment of the present specification, Chemical Formula 1 is represented by the following Chemical Formula 1-1.

[Formula 1-1]

In Formula 1-1,

The definitions of R1, R2, Ar1 and X1 are the same as those defined in Formula 1 above.

According to an exemplary embodiment of the present specification, in Formula 1, X1 is S.

According to an exemplary embodiment of the present specification, in Formula 1, X1 is O.

According to an exemplary embodiment of the present specification, Chemical Formula 1 is represented by the following Chemical Formula 1-2 or 1-3.

[Formula 1-2]

[Formula 1-3]

In Formulas 1-2 and 1-3,

Definitions of R1 to R5, r3 to r5 and Ar1 are the same as those defined in Formula 1 above.

According to an exemplary embodiment of the present specification, Chemical Formula 1 is represented by the following Chemical Formulas 1-4 or 1-5.

[Formula 1-4]

[Formula 1-5]

In Formulas 1-4 and 1-5,

Definitions of R1, R2 and Ar1 are the same as those defined in Formula 1 above.

According to an exemplary embodiment of the present specification, in Formula 1, at least one of R1 and R2 is a substituted or unsubstituted aryl group, the rest is a substituted or unsubstituted alkyl group; or a substituted or unsubstituted aryl group.

According to an exemplary embodiment of the present specification, since Formula 1 specifically includes a compound in which at least one of R1 and R2 is a substituted or unsubstituted aryl group, the molecular weight of the compound in which both R1 and R2 is an alkyl group increases, free The high transition temperature (Tg) has thermal stability, and the organic light emitting device using the same for the organic material layer has effects of low voltage, high efficiency and long life.

According to an exemplary embodiment of the present specification, in Formula 1, at least one of R1 and R2 is a monocyclic or polycyclic aryl group having 6 to 30 carbon atoms that is unsubstituted or substituted with a linear or branched alkyl group having 1 to 30 carbon atoms. and the rest is a linear or branched alkyl group having 1 to 30 carbon atoms; or a C6-C30 monocyclic or polycyclic aryl group unsubstituted or substituted with a C1-C30 linear or branched alkyl group.

According to an exemplary embodiment of the present specification, in Formula 1, at least one of R1 and R2 is a monocyclic or polycyclic aryl group having 6 to 20 carbon atoms that is unsubstituted or substituted with a linear or branched alkyl group having 1 to 20 carbon atoms. and the remainder is a linear or branched alkyl group having 1 to 20 carbon atoms; or a monocyclic or polycyclic aryl group having 6 to 20 carbon atoms which is unsubstituted or substituted with a linear or branched alkyl group having 1 to 20 carbon atoms.

According to an exemplary embodiment of the present specification, in Formula 1, at least one of R1 and R2 is a monocyclic or polycyclic aryl group having 6 to 10 carbon atoms that is unsubstituted or substituted with a linear or branched alkyl group having 1 to 10 carbon atoms. and the remainder is a linear or branched alkyl group having 1 to 10 carbon atoms; or a monocyclic or polycyclic aryl group having 6 to 10 carbon atoms that is unsubstituted or substituted with a linear or branched alkyl group having 1 to 10 carbon atoms.

According to an exemplary embodiment of the present specification, in Formula 1, at least one of R1 and R2 is a phenyl group unsubstituted or substituted with a methyl group, and the remainder is a methyl group; or a phenyl group unsubstituted or substituted with a methyl group.

According to an exemplary embodiment of the present specification, in Formula 1, at least one of R1 and R2 is a phenyl group; or a phenyl group substituted with a methyl group, the remainder being a methyl group; phenyl group; or a phenyl group substituted with a methyl group.

According to an exemplary embodiment of the present specification, in Formula 1, R1 and R2 are the same as or different from each other, and each independently a linear or branched alkyl group having 1 to 30 carbon atoms; or a C6-C30 monocyclic or polycyclic aryl group unsubstituted or substituted with a C1-C30 linear or branched alkyl group.

According to an exemplary embodiment of the present specification, in Formula 1, R1 and R2 are the same as or different from each other, and each independently a linear or branched alkyl group having 1 to 20 carbon atoms; or a monocyclic or polycyclic aryl group having 6 to 20 carbon atoms which is unsubstituted or substituted with a linear or branched alkyl group having 1 to 20 carbon atoms.

According to an exemplary embodiment of the present specification, in Formula 1, R1 and R2 are the same as or different from each other, and each independently a linear or branched alkyl group having 1 to 10 carbon atoms; or a monocyclic or polycyclic aryl group having 6 to 10 carbon atoms that is unsubstituted or substituted with a linear or branched alkyl group having 1 to 10 carbon atoms.

According to an exemplary embodiment of the present specification, in Formula 1, R1 and R2 are external or different from each other, and each independently a methyl group; or a phenyl group unsubstituted or substituted with a methyl group.

According to an exemplary embodiment of the present specification, in Formula 1, R1 and R2 are methyl groups.

According to an exemplary embodiment of the present specification, in Formula 1, R1 and R2 are phenyl groups.

According to an exemplary embodiment of the present specification, in Formula 1, R1 and R2 are a phenyl group substituted with a methyl group.

According to an exemplary embodiment of the present specification, in Formula 1, R1 is a methyl group, and R2 is a phenyl group.

According to an exemplary embodiment of the present specification, in Formula 1, R1 is a methyl group, and R2 is a phenyl group substituted with a methyl group.

According to an exemplary embodiment of the present specification, in Formula 1, R1 is a phenyl group, and R2 is a phenyl group substituted with a methyl group.

According to an exemplary embodiment of the present specification, in Formula 1, R2 is a methyl group, and R1 is a phenyl group.

According to an exemplary embodiment of the present specification, in Formula 1, R2 is a methyl group, and R1 is a phenyl group substituted with a methyl group. According to an exemplary embodiment of the present specification, in Formula 1, R2 is a phenyl group, and R1 is a phenyl group substituted with a methyl group.

According to an exemplary embodiment of the present specification, in Formula 1, Ar1 is a linear or branched alkyl group having 1 to 30 carbon atoms, a monocyclic or polycyclic aryl group having 6 to 30 carbon atoms, or a monocyclic or polycyclic group having 2 to 30 carbon atoms. a monocyclic or polycyclic aryl group having 6 to 30 carbon atoms that is unsubstituted or substituted with a cyclic heteroaryl group; or a monocyclic or polycyclic heteroaryl group having 2 to 30 carbon atoms that is unsubstituted or substituted with a monocyclic or polycyclic aryl group having 6 to 30 carbon atoms.

According to an exemplary embodiment of the present specification, in Formula 1, Ar1 is a linear or branched alkyl group having 1 to 20 carbon atoms, a monocyclic or polycyclic aryl group having 6 to 20 carbon atoms, or a monocyclic or polycyclic group having 2 to 20 carbon atoms. a monocyclic or polycyclic aryl group having 6 to 20 carbon atoms that is unsubstituted or substituted with a cyclic heteroaryl group; or a monocyclic or polycyclic heteroaryl group having 2 to 20 carbon atoms that is unsubstituted or substituted with a monocyclic or polycyclic aryl group having 6 to 20 carbon atoms.

According to an exemplary embodiment of the present specification, in Formula 1, Ar1 is a phenyl group unsubstituted or substituted with a monocyclic or polycyclic aryl group having 6 to 30 carbon atoms, or a monocyclic or polycyclic heteroaryl group having 2 to 30 carbon atoms; biphenyl group; naphthyl group; terphenyl group; triphenylene group; a fluorene group unsubstituted or substituted with a linear or branched alkyl group having 1 to 30 carbon atoms; pyridine group; a triazine group unsubstituted or substituted with a monocyclic or polycyclic aryl group having 6 to 30 carbon atoms; a carbazole group unsubstituted or substituted with a monocyclic or polycyclic aryl group having 6 to 30 carbon atoms; dibenzofuran group; or a dibenzothiophene group.

According to an exemplary embodiment of the present specification, in Formula 1, Ar1 is a phenyl group unsubstituted or substituted with a monocyclic or polycyclic aryl group having 6 to 20 carbon atoms, or a monocyclic or polycyclic heteroaryl group having 2 to 20 carbon atoms; biphenyl group; naphthyl group; terphenyl group; triphenylene group; a fluorene group unsubstituted or substituted with a linear or branched alkyl group having 1 to 20 carbon atoms; pyridine group; a triazine group unsubstituted or substituted with a monocyclic or polycyclic aryl group having 6 to 20 carbon atoms; a carbazole group unsubstituted or substituted with a monocyclic or polycyclic aryl group having 6 to 20 carbon atoms; dibenzofuran group; or a dibenzothiophene group.

According to an exemplary embodiment of the present specification, in Formula 1, Ar1 is a phenyl group unsubstituted or substituted with a naphthyl group, a carbazole group, or a quinoline group; biphenyl group; naphthyl group; terphenyl group; triphenylene group; a fluorene group unsubstituted or substituted with a methyl group; pyridine group; a triazine group unsubstituted or substituted with a phenyl group; a carbazole group unsubstituted or substituted with a phenyl group; dibenzofuran group; or a dibenzothiophene group.

According to an exemplary embodiment of the present specification, in Formula 1, Ar1 is a phenyl group unsubstituted or substituted with a naphthyl group, a carbazole group, or a quinoline group; biphenyl group; naphthyl group; terphenyl group; triphenylene group; a fluorene group substituted with a methyl group; pyridine group; a triazine group substituted with a phenyl group; a carbazole group substituted with a phenyl group; dibenzofuran group; or a dibenzothiophene group.

According to an exemplary embodiment of the present specification, Formula 1 is selected from the following compounds.

According to an exemplary embodiment of the present specification, there is provided an organic light emitting device including the heterocyclic compound represented by Formula 1 above.

According to an exemplary embodiment of the present specification, the first electrode; a second electrode provided to face the first electrode; and at least one organic material layer provided between the first electrode and the second electrode, wherein at least one layer of the organic material layer includes the above-described heterocyclic compound.

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 the present 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.

According to an exemplary embodiment of the present specification, the organic material layer of the organic light emitting device of the present specification may have a single-layer structure, but may have a multi-layer structure in which two or more organic material layers are stacked. For example, the organic light emitting device of the present invention may have a structure including a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron electron injection layer, etc. as an organic material layer. However, the structure of the organic light emitting device is not limited thereto and may include a smaller or larger number of organic layers.

For example, the structure of the organic light emitting device of the present specification 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 10 in which a first electrode 30 , a light emitting layer 40 , and a second electrode 50 are sequentially stacked on a substrate 20 . 2, the first electrode 30, the hole injection layer 60, the hole transport layer 70, the electron blocking layer 80, the light emitting layer 40, the hole blocking layer 90, the electrons on the substrate 20 The structure of the organic light-emitting device 11 in which the layer 100 and the second electrode 50 for injection and transport are sequentially stacked is exemplified. 1 and 2 are exemplary structures of an organic light emitting device according to an exemplary embodiment of the present specification, and may further include another organic material layer.

According to an exemplary embodiment of the present specification, the organic material layer includes an emission layer, and the emission layer includes the heterocyclic compound.

According to an exemplary embodiment of the present specification, the organic material layer includes an emission layer, and the emission layer includes the heterocyclic compound as a host of the emission layer.

According to an exemplary embodiment of the present specification, the organic material layer includes a hole blocking layer, and the hole blocking layer includes the heterocyclic compound.

According to an exemplary embodiment of the present specification, the organic material layer includes an electron injection layer, an electron transport layer, or a layer that simultaneously injects and transports electrons, and the electron injection layer, the electron transport layer, or a layer that simultaneously injects and transports electrons and the heterocyclic compound.

According to an exemplary embodiment of the present specification, the organic material layer includes an electron injection layer, and the electron injection layer includes the heterocyclic compound.

According to an exemplary embodiment of the present specification, the organic material layer includes an electron transport layer, and the electron transport layer includes the heterocyclic compound.

According to an exemplary embodiment of the present specification, the organic material layer includes a layer for simultaneously injecting and transporting electrons, and the layer for simultaneously injecting and transporting electrons includes the heterocyclic compound.

According to an exemplary embodiment of the present specification, the organic material layer may further include one or more layers selected from the group consisting of a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, and an electron injection layer. .

The organic light emitting device of the present specification may be manufactured by materials and methods known in the art, except that at least one layer of the organic material layer contains the heterocyclic compound of the present specification, that is, the heterocyclic compound represented by Formula 1 above. can

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.

For example, the organic light emitting device of the present specification may be manufactured by sequentially stacking a first electrode, an organic material layer, and a second electrode on a substrate. At this time, by using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation, a metal or a metal oxide having conductivity or an alloy thereof is deposited on the substrate. It may be manufactured by forming a first electrode, forming an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer thereon, and then depositing a material that can be used as the second electrode thereon. In addition to the above method, an organic light emitting device may be manufactured by sequentially depositing a second electrode material, an organic material layer, and a first electrode material on a substrate. In addition, the heterocyclic compound represented by Formula 1 may be formed into an organic material layer by a solution coating method as well as a vacuum deposition method when manufacturing an organic light emitting device. Here, the solution application method refers to spin coating, dip coating, doctor blading, inkjet printing, screen printing, spray method, roll coating, and the like, but is not limited thereto.

According to an exemplary embodiment of the present specification, the first electrode is an anode, and the second electrode is a cathode.

According to another exemplary embodiment of the present specification, the first electrode is a cathode, and the second electrode is an anode.

As the anode material, a material having a large work function is generally preferable to facilitate hole injection 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; 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 negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead, or alloys thereof; LiF/Al or LiO ₂ /Al, and a multi-layered material such as Mg/Ag, but is not limited thereto.

The hole injection layer is a layer for injecting holes from the electrode as a hole injection material, and has an ability to transport holes as a hole injection material, so that it has an excellent hole injection effect with respect to the hole injection effect at the anode, the light emitting layer or the light emitting material. , a compound that prevents the movement of excitons generated in the light emitting layer to the electron injection layer or the electron injection material and is excellent in the ability to form a thin film is preferable. It is preferable that the highest occupied molecular orbital (HOMO) of the hole injection material is between the work function of the positive electrode material and the HOMO of the surrounding organic material layer. Specific examples of the hole injection material include metal porphyrin, oligothiophene, arylamine-based organic material, hexanitrile hexaazatriphenylene-based organic material, quinacridone-based organic material, and perylene-based organic material. of organic substances, anthraquinones, and conductive polymers of polyaniline and polythiophene series, but are not limited thereto.

The hole transport layer is a layer that receives holes from the hole injection layer and transports them to the light emitting layer. The hole transport material is a material that can transport holes from the anode or the hole injection layer to the light emitting layer and transfer them to the light emitting layer. material 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 electron blocking layer is a layer that can improve the life and efficiency of the device by preventing the electrons injected from the electron injection layer from entering the hole injection layer through the light emitting layer, and, if necessary, using a known material to form the light emitting layer and the hole It may be formed in an appropriate portion between the injection layers.

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

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

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

The hole blocking layer is a layer capable of improving the lifespan and efficiency of the device by preventing holes injected from the hole injection layer from entering the electron injection layer through the light emitting layer, and the organic light emitting device of the present specification is represented by Formula 1 In the case of including an additional hole blocking layer in addition to the hole blocking layer containing the heterocyclic compound, it may be formed in an appropriate portion between the light emitting layer and the electron injection layer using a known material, if necessary.

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

The electron injection layer is a layer that injects electrons from the electrode, and when the organic light emitting device of the present specification includes an additional electron injection layer in addition to the electron injection layer including the heterocyclic compound represented by Formula 1, electrons are injected A compound that has the ability to transport, has an electron injection effect from the cathode, has an excellent electron injection effect with respect to the light emitting layer or light emitting material, prevents movement of excitons generated in the light emitting layer to the hole injection layer, and has excellent thin film forming ability This is preferable. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene 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 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.

According to an exemplary embodiment of the present specification, the heterocyclic compound represented by Formula 1 may be included in an organic solar cell or an organic transistor in addition to the organic light emitting device.

Hereinafter, examples will be given to describe the present specification in detail. However, the embodiments according to the present specification may be modified in various other forms, and the scope of the present specification is not to be construed as being limited to the embodiments described below. The embodiments of the present specification are provided to more completely explain the present specification to those of ordinary skill in the art.

The starting material of the following preparation example according to an exemplary embodiment of the present specification may be prepared by the following general formula 1, but is not limited thereto.

[General formula 1]

manufacturing example

<Production Example 1>

[Compound 1]

Compound A (4.50 g, 7.20 mmol) and compound a-1 (2.17 g, 7.56 mmol) were completely dissolved in 240 ml of tetrahydrofuran in a 500 ml round bottom flask in a nitrogen atmosphere, and 2M aqueous potassium carbonate solution (120 ml) was added thereto, and tetrahydrofuran was added. Kis- (triphenylphosphine) palladium (0.25 g, 0.22 mmol) was added, followed by heating and stirring for 4 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized from 220 ml of ethyl acetate to prepare Compound 1 (3.87 g, 65%).

MS[M+H] ⁺ = 833

<Production Example 2>

[Compound 2]

Compound A (4.50 g, 7.20 mmol) and compound a-2 (1.50 g, 7.56 mmol) were completely dissolved in 200 ml of tetrahydrofuran in a 500 ml round bottom flask in a nitrogen atmosphere, and then 2M aqueous potassium carbonate solution (100 ml) was added, and tetra Kis- (triphenylphosphine) palladium (0.25 g, 0.22 mmol) was added, followed by heating and stirring for 2 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized from 170 ml of ethyl acetate to prepare compound 2 (3.17 g, 59%).

MS[M+H] ⁺ = 744

<Production Example 3>

[Compound 3]

Compound A (4.50 g, 7.20 mmol) and compound a-3 (1.30 g, 7.56 mmol) were completely dissolved in 220 ml of tetrahydrofuran in a 500 ml round bottom flask in a nitrogen atmosphere, and then 2M aqueous potassium carbonate solution (110 ml) was added, and tetrahydrofuran was added. Kis- (triphenylphosphine) palladium (0.25 g, 0.22 mmol) was added, followed by heating and stirring for 2 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized from 290 ml of ethyl acetate to prepare compound 3 (3.57 g, 69%).

MS[M+H] ⁺ = 718

<Production Example 4>

[Compound 4]

Compound A (4.50 g, 7.20 mmol) and compound a-4 (0.92 g, 7.56 mmol) were completely dissolved in 260 ml of tetrahydrofuran in a 500 ml round bottom flask in a nitrogen atmosphere, and 2M aqueous potassium carbonate solution (130 ml) was added thereto, and tetrahydrofuran was added. Kis- (triphenylphosphine) palladium (0.25 g, 0.22 mmol) was added, followed by heating and stirring for 4 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized from 250 ml of ethyl acetate to prepare compound 4 (2.86 g, 59%).

MS[M+H] ⁺ = 668

<Preparation Example 5>

[Compound 5]

Compound B (4.50 g, 7.39 mmol) and compound a-5 (2.23, 7.76 mmol) were completely dissolved in 180 ml of tetrahydrofuran in a 500 ml round bottom flask in a nitrogen atmosphere, and 2M aqueous potassium carbonate solution (90 ml) was added thereto, and tetrakis -(triphenylphosphine)palladium (0.26g, 0.22mmol) was added, and the mixture was heated and stirred for 6 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized from 130 ml of tetrahydrofuran to prepare compound 5 (3.02 g, 69%).

MS[M+H] ⁺ = 592

<Preparation Example 6>

[Compound 6]

Compound B (4.50 g, 7.39 mmol) and compound a-6 (1.54 g, 7.76 mmol) were completely dissolved in 200 ml of tetrahydrofuran in a 500 ml round bottom flask in a nitrogen atmosphere, and 2M aqueous potassium carbonate solution (100 ml) was added, and tetrahydrofuran was added. Kis- (triphenylphosphine) palladium (0.26 g, 0.22 mmol) was added, followed by heating and stirring for 6 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized from 190 ml of tetrahydrofuran to prepare compound 6 (4.13 g, 77%).

MS[M+H] ⁺ = 742

<Production Example 7>

[Compound 7]

Compound B (4.50 g, 7.39 mmol) and compound a-7 (1.33 g, 7.76 mmol) were completely dissolved in 220 ml of tetrahydrofuran in a 500 ml round bottom flask in a nitrogen atmosphere, and 2M aqueous potassium carbonate solution (110 ml) was added thereto, and tetrahydrofuran Kis- (triphenylphosphine) palladium (0.26 g, 0.22 mmol) was added, followed by heating and stirring for 2 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized from 160 ml of tetrahydrofuran to prepare compound 7 (3.24 g, 62%).

MS[M+H] ⁺ = 702

<Preparation Example 8>

[Compound 8]

Compound B (4.50 g, 7.39 mmol) and compound a-8 (1.82 g, 7.76 mmol) were completely dissolved in 400 ml of tetrahydrofuran in a 500 ml round bottom flask in a nitrogen atmosphere, and 2M aqueous potassium carbonate solution (200 ml) was added, and tetrahydrofuran was added. Kis- (triphenylphosphine) palladium (0.26 g, 0.22 mmol) was added, followed by heating and stirring for 4 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized from 110 ml of tetrahydrofuran to prepare compound 8 (3.47 g, 61%).

MS[M+H] ⁺ = 758

Fabrication of organic light emitting devices

Comparative Example 1

A glass substrate coated with indium tin oxide (ITO) 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, dried, and then transported to a plasma cleaner. In addition, after cleaning the substrate for 5 minutes using oxygen plasma, the substrate was transported to a vacuum evaporator.

The following compound HI-1 was formed to a thickness of 1150 Å as a hole injection layer on the prepared ITO transparent electrode, but the following compound A-1 was p-doped at a concentration of 1.5%. The following compound HT-1 was vacuum-deposited on the hole injection layer to form a hole transport layer having a thickness of 800 Å. Then, the following compound EB-1 was vacuum-deposited to a film thickness of 150 Å on the hole transport layer to form an electron blocking layer. Subsequently, the following compound RH-1 and the following compound Dp-7 were vacuum-deposited in a weight ratio of 98:2 on the compound EB-1 deposited layer to form a red light emitting layer having a thickness of 400 Å. A hole blocking layer was formed by vacuum-depositing the following compound HB-1 to a thickness of 30 Å on the light emitting layer. Then, on the hole blocking layer, the following compound ET-1 and the following compound LiQ were vacuum-deposited at a weight ratio of 2:1 to form an electron injection and transport layer to a thickness of 300 Å. A cathode was formed by sequentially depositing lithium fluoride (LiF) to a thickness of 12 Å and aluminum to a thickness of 1,000 Å on the electron injection and transport layer.

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

Examples 1 to 8

An organic light emitting device was manufactured in the same manner as in Comparative Example 1, except that the compound shown in Table 1 was used instead of RH-1 in the organic light emitting device of Comparative Example 1.

Comparative Examples 2 to 4

An organic light emitting device was manufactured in the same manner as in Comparative Example 1, except that the compound shown in Table 1 was used instead of RH-1 in the organic light emitting device of Comparative Example 1.

device evaluation

When a current was applied to the organic light emitting devices prepared in Examples 1 to 8 and Comparative Examples 1 to 4, voltage, efficiency, and lifetime were measured, and the results are shown in Table 1 below. T95 denotes the time required for the luminance to decrease from the initial luminance (5000 nit) to 95%.

division compound Driving voltage (V) Efficiency (cd/A) Life T95 (hr) luminous color Comparative Example 1 RH-1 4.57 33.1 192 Red Example 1 compound 1 4.34 35.2 223 Red Example 2 compound 2 4.38 36.4 276 Red Example 3 compound 3 4.09 39.1 257 Red Example 4 compound 4 3.99 40.2 264 Red Example 5 compound 5 4.03 37.8 255 Red Example 6 compound 6 4.06 39.5 251 Red Example 7 compound 7 4.19 37.3 269 Red Example 8 compound 8 4.16 38.1 248 Red Comparative Example 2 RH-2 4.54 34.9 137 Red Comparative Example 3 RH-3 4.61 33.6 156 Red Comparative Example 4 RH-4 4.52 33.9 153 Red

When a current was applied to the organic light emitting diodes fabricated in Examples 1 to 8 and Comparative Examples 1 to 4, the results shown in Table 1 were obtained. The red organic light emitting device of Comparative Example 1 used a conventionally widely used material, and had a structure using compound [EB-1] as an electron blocking layer and RH-1/Dp-7 as a red light emitting layer. In Comparative Examples 2 to 4, an organic light emitting device was manufactured by using any one of RH-2 to RH-4 instead of RH-1. From the results of Table 1, when the compound of Formula 1 according to an exemplary embodiment of the present specification was used as a host for the red light emitting layer of the organic light emitting device, the driving voltage was lowered by up to 20% compared to Comparative Examples 1 to 4, and the efficiency From the side view, it can be seen that the energy transfer from the host to the red dopant is well performed, as it is seen that the increase is more than 20%. In addition, it was found that the organic light emitting devices of Examples 1 to 8 can significantly improve lifespan characteristics by 1.5 times or more than those of the organic light emitting devices of Comparative Examples 1 to 4 while maintaining high efficiency. The above result could be determined because the compound of Formula 1 according to an exemplary embodiment of the present specification has higher stability for electrons and holes than RH-1 to RH-4. Therefore, it was confirmed that when the compound of Formula 1 according to an exemplary embodiment of the present specification was used as a host of the red light emitting layer of the organic light emitting device, the driving voltage, luminous efficiency, and lifespan characteristics of the organic light emitting device could be improved.

Although the preferred embodiment (red light emitting layer) of the present invention has been described above, the present invention is not limited thereto, and various modifications can be made within the scope of the claims and the detailed description of the invention, and this belongs to the category of

10, 11: organic light emitting device
20: substrate
30: first electrode
40: light emitting layer
50: second electrode
60: hole injection layer
70: hole transport layer
80: electron blocking layer
90: hole blocking layer
100: a layer that simultaneously injects and transports electrons

Claims (11)

A heterocyclic compound represented by the following formula (1):
[Formula 1]

In Formula 1,
X1 is O or S;
At least one of R1 and R2 is a substituted or unsubstituted aryl group, and the remainder is a substituted or unsubstituted alkyl group; Or a substituted or unsubstituted aryl group,
Ar1 is a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,
R3 to R5 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,
r3 to r5 are each an integer of 1 to 4,
When r3 is 2 or more, two or more of R3 are the same as or different from each other,
When r4 is 2 or more, two or more of R4 are the same as or different from each other,
When r5 is 2 or more, two or more of R5 are the same as or different from each other,
The "substituted or unsubstituted" is deuterium; halogen group; cyano group; an alkyl group; cycloalkyl group; alkenyl group; alkoxy group; aryloxy group; aryl group; and substituted with one or more substituents selected from the group consisting of a heteroaryl group, or substituted with a substituent to which two or more substituents are connected among the substituents, or does not have any substituents. The heterocyclic compound according to claim 1, wherein Chemical Formula 1 is represented by the following Chemical Formula 1-2 or 1-3:
[Formula 1-2]

[Formula 1-3]

In Formulas 1-2 and 1-3,
Definitions of R1 to R5, r3 to r5 and Ar1 are the same as those defined in Formula 1 above. The heterocyclic compound according to claim 1, wherein Chemical Formula 1 is represented by the following Chemical Formulas 1-4 or 1-5:
[Formula 1-4]

[Formula 1-5]

In Formulas 1-4 and 1-5,
Definitions of R1, R2 and Ar1 are the same as those defined in Formula 1 above. The method according to claim 1, wherein at least one of R1 and R2 is a monocyclic or polycyclic aryl group having 6 to 30 carbon atoms that is unsubstituted or substituted with a straight-chain or branched alkyl group having 1 to 30 carbon atoms, and the remainder is a C1-C30 alkyl group. a straight-chain or branched alkyl group; Or a heterocyclic compound that is a monocyclic or polycyclic aryl group having 6 to 30 carbon atoms that is unsubstituted or substituted with a linear or branched alkyl group having 1 to 30 carbon atoms. The method according to claim 1, wherein Ar1 is a linear or branched alkyl group having 1 to 30 carbon atoms, a monocyclic or polycyclic aryl group having 6 to 30 carbon atoms, or a monocyclic or polycyclic heteroaryl group having 2 to 30 carbon atoms, substituted or unsubstituted a monocyclic or polycyclic aryl group having 6 to 30 carbon atoms; Or a heterocyclic compound that is a monocyclic or polycyclic heteroaryl group having 2 to 30 carbon atoms that is unsubstituted or substituted with a monocyclic or polycyclic aryl group having 6 to 30 carbon atoms. The heterocyclic compound according to claim 1, wherein Chemical Formula 1 is selected from the following compounds:

a first electrode;
a second electrode provided to face the first electrode; and
An organic light emitting device including at least one organic material layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes the heterocyclic compound of any one of claims 1 to 6 . The organic light-emitting device of claim 7 , wherein the organic material layer includes an emission layer, and the emission layer includes the heterocyclic compound. The organic light-emitting device of claim 7 , wherein the organic material layer includes an emission layer, and the emission layer includes the heterocyclic compound as a host of the emission layer. The organic light-emitting device of claim 7 , wherein the organic material layer includes a hole blocking layer, and the hole blocking layer includes the heterocyclic compound. The method according to claim 7, wherein the organic layer comprises an electron injection layer, an electron transport layer, or a layer that simultaneously injects and transports electrons, and the electron injection layer, the electron transport layer, or a layer that simultaneously injects and transports electrons is the heterocyclic compound An organic light emitting device comprising a.

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