KR102107874B1 - Hetero-cyclic compound and organic light emitting device comprising the same - Google Patents

Abstract

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

Description

A heterocyclic compound and an organic light emitting device comprising the same {HETERO-CYCLIC 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 that converts electrical energy into light energy using an organic material. An organic light emitting device using an organic light emitting phenomenon usually has a structure including an anode and a cathode and an organic material layer therebetween. Here, in order to increase the efficiency and stability of the organic light emitting device, the organic material layer is often composed of a multi-layered structure composed of different materials, for example, may be formed of 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 at the anode, and electrons are injected at the cathode, and an exciton is formed when the injected holes meet the electrons. When it falls to the ground again, it will shine.

The development of new materials for such organic light-emitting devices continues to be required.

US Patent Application Publication No. 2004-0251816

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

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

[Formula 1]

In Chemical Formula 1,

X1 is N or CR,

X2 is N or CR ',

However, X1 and X2 are not N at the same time,

R and R 'are the same as or different from each other, and each independently hydrogen; Cyano group; A substituted or unsubstituted haloaryl group; A substituted or unsubstituted cyanoaryl group; Or a substituted or unsubstituted N-containing heteroaryl group,

R1 to R4 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; Cyano group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted haloalkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted haloalkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted aralkyl group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted alkylsilyl group; A substituted or unsubstituted arylsilyl group; A substituted or unsubstituted cyanoaryl group; A substituted or unsubstituted alkylaryl group; A substituted or unsubstituted haloalkylaryl group; A substituted or unsubstituted aryl group; A substituted or unsubstituted haloaryl group; Or a substituted or unsubstituted heterocyclic group, or at least one of R1 and R2 and R3 and R4 may be bonded to each other to form a substituted or unsubstituted ring.

In addition, an exemplary embodiment of the present specification is 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 at least one layer of the organic material layer includes a heterocyclic compound represented by Chemical Formula 1 above. Provides

The heterocyclic compound described herein can be used as a material for the organic material layer of the organic light emitting device. The heterocyclic compound according to at least one exemplary embodiment may improve efficiency, low driving voltage, and / or lifespan characteristics in an organic light emitting device. In particular, the compounds described herein can be used as hole injection, hole transport, hole injection and hole transport, luminescence, electron transport, or electron injection materials. In addition, the heterocyclic compound described in this specification may be preferably used as a light emitting layer, electron transport or electron injection material. In addition, more preferably, the heterocyclic compound described herein exhibits characteristics of low voltage, high efficiency and / or long life when used as a material for hole injection, hole transport, electron suppression layer or charge generation layer.

FIG. 1 shows an example of an organic light emitting device comprising a substrate 1, an anode 2, a hole transport layer 6, a light emitting layer 3, and a cathode 4.
2 shows an example of an organic light-emitting device comprising a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light emitting layer 3, an electron transport layer 8 and a cathode 4 It is done.
3 includes a substrate 1, an anode 2 and a cathode 4, between the anode and the cathode, hole injection layers 5a, 5b, hole transport layers 6a, 6b, light emitting layers 3a, 3b And two units including the electron transport layers 8a and 8b, and showing an example of an organic light emitting device in which the charge generation layer 9 is provided between the units.
4 is a diagram showing HLPC analysis data of Compound 4 according to an exemplary embodiment of the present specification.
5 is a diagram showing Mass Analysis data of Compound 4 according to an exemplary embodiment of the present specification.
6 is a diagram showing HLPC analysis data of Compound 16 according to an exemplary embodiment of the present specification.
7 is a view showing Mass Analysis data of Compound 16 according to an exemplary embodiment of the present specification.
8 is a view showing current densities according to driving voltages of Examples 1 and 2 and Comparative Example 1 according to an exemplary embodiment of the present specification.

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

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

The heterocyclic compound represented by Chemical Formula 1 according to an exemplary embodiment of the present specification is a thin film such as optimizing an electronic state such as enhancing stability through a pyrazinoquinazoline core structure, or suppressing crystallization by changing a three-dimensional structure of a molecule. Since the state can be changed, the performance of the organic light emitting device can be improved. That is, since the heterocyclic compound represented by Chemical Formula 1 according to an exemplary embodiment of the present specification has high electron acceptability and can form a good thin film, it is possible to drive low voltage and provide a long-life organic light emitting device. It is possible.

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

The term "substituted or unsubstituted" as used herein refers to deuterium; Halogen group; Cyano group; Alkoxy groups; Haloalkoxy groups; Aryloxy group; Alkyl groups; Haloalkyl group; Cycloalkyl group; Alkenyl group; Haloaryl group; Aralkyl group; An alkenyl group; Alkyl aryl groups; Haloalkylaryl group; Aryl group; And substituted or unsubstituted with one or more substituents selected from the group consisting of heterocyclic groups, or substituted or unsubstituted with two or more substituents among the exemplified substituents. For example, "a substituent having two or more substituents" may be a biphenyl group. That is, the biphenyl group may be an aryl group or may be interpreted as a substituent to 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 straight chain or branched chain, and carbon number is not particularly limited, but is preferably 1 to 40. According to an exemplary embodiment, the alkyl group has 1 to 20 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 10 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 6 carbon atoms. Specific examples of the alkyl group are methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n -Pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl , n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2 -Dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 4-methylhexyl, 5-methylhexyl, and the like, but is not limited thereto.

In the present specification, the alkenyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to one embodiment, the carbon number of the alkenyl group is 2 to 20. According to another exemplary embodiment, the alkenyl group has 2 to 10 carbon atoms. According to another exemplary embodiment, the alkenyl group has 2 to 6 carbon atoms. Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1- Butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2- ( Naphthyl-1-yl) vinyl-1-yl, 2,2-bis (diphenyl-1-yl) vinyl-1-yl, steelbenyl group, styrenyl group, and the like, but are not limited thereto.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and according to an exemplary embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another exemplary embodiment, the cycloalkyl group has 3 to 20 carbon atoms. According to another exemplary embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specifically, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3, 4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like, but is not limited thereto.

In the present specification, the alkoxy group is not particularly limited, but is preferably 1 to 40 carbon atoms. According to one embodiment, the carbon number of the alkoxy group is 1 to 10. According to another exemplary embodiment, the alkoxy group has 1 to 6 carbon atoms. Specific examples of the alkoxy group include, but are not limited to, methoxy group, ethoxy group, propoxy group, isobutyloxy group, sec-butyloxy group, pentyloxy group, iso-amyloxy group, hexyloxy group, and the like.

In the present specification, the aryl group is not particularly limited, but is preferably 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the carbon number of the aryl group is 6 to 30. According to one embodiment, the carbon number of the aryl group is 6 to 20. The aryl group may be a phenyl group, a biphenyl group, a terphenyl group, etc., as a monocyclic aryl group, but is not limited thereto. The polycyclic aryl group may be a naphthyl group, anthracenyl group, phenanthryl group, pyrenyl group, perylene group, chrysenyl group, fluorenyl group, triphenylene group, etc., 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.

In the present specification, the “adjacent” group refers to a substituent substituted on an atom directly connected to an atom in which the substituent is substituted, a substituent positioned closest to the substituent and the other substituent substituted on the atom in which the substituent is substituted. You can. For example, two substituents substituted in the ortho position on the benzene ring and two substituents substituted on the same carbon in the aliphatic ring may be interpreted as "adjacent" groups to each other.

,

,

,

,

,

,

및

등이 될 수 있다. 다만, 이에 한정되는 것은 아니다.When the fluorenyl group is substituted,

,

,

,

,

,

,

And

It can be back. However, it is not limited thereto.

In the present specification, the heterocyclic group is a heteroatom as a heterocyclic group containing one or more of N, O, S, Si, and Se, and the number of carbon atoms is not particularly limited, but is preferably 2 to 60 carbon atoms. Examples of the heterocyclic group include thiophene group, furan group, pyrrol group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, pyrimidyl group, triazine group, triazole group, Acridil group, carboline group, acenaphthoquinoxaline group, indenoquinazoline, indenoisoquinoline group, indenoquinoline group, pyridoindol group, pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group , Quinoxalinyl group, phthalazinyl group, pyrido pyrimidinyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group, isoquinoline group, indole group, carbazole group, benzoxazole group, benzimidazole group, benzothiazole group , Benzocarbazole, Benzothiophene group, dibenzothiophene group, benzofuran group, dibenzofuran group, phenanthroline group, thiazolyl group, isooxazolyl group, oxadiazolyl group, thiadiazolyl group, benzothiazolyl group , Phenoxazinyl group, phenothiazinyl group and dibenzofuranyl group, but are not limited to these. The heterocyclic group includes an aliphatic heterocyclic group and an aromatic heterocyclic group.

In the present specification, the aryl group in the aralkyl group, the alkenyl group, the aryloxy group, the alkylaryl group, the haloaryl group, the haloalkylaryl group, the arylsilyl group, and the cyanoaryl group may be applied to the aryl group described above.

In the present specification, the alkyl group among the aralkyl group, alkylaryl group, haloalkyl group, haloalkylaryl group, and alkylsilyl group may be applied to the above-described alkyl group.

In the present specification, the alkenyl group among the alkenyl groups may be applied to the alkenyl group described above.

In the present specification, the description of the alkoxy group described above may be applied to the alkoxy group among the haloalkoxy groups.

In the present specification, a haloalkyl group, a haloalkoxy group, a haloalkylaryl group, and a haloaryl group mean an alkyl group, an alkoxy group, an alkylaryl group, and an aryl group, each substituted with halogen.

In the present specification, a cyanoaryl group means an aryl group substituted with one or more cyano groups.

In the present specification, the alkylsilyl group means a silyl group substituted with an alkyl group, and the arylsilyl group means a silyl group substituted with an aryl group, and may be represented by -SiR ₁₀₀ R ₁₀₁ R ₁₀₂ , where R ₁₀₀ , R ₁₀₁ and R ₁₀₂ are the same as or different from each other, and each independently an alkyl group or an aryl group. Here, the description of the alkyl group and the aryl group may be applied to the aforementioned alkyl group and aryl group, respectively.

In the present specification, the ring is a substituted or unsubstituted hydrocarbon ring; Or a substituted or unsubstituted hetero ring.

In the present specification, the hydrocarbon ring may be an aromatic, aliphatic or aromatic and aliphatic condensed ring, and may be selected from examples of the cycloalkyl group or aryl group except for the non-monovalent.

In the present specification, the aromatic ring may be monocyclic or polycyclic, and may be selected from examples of the aryl group, except that it is not monovalent.

In the present specification, the heterocycle includes one or more non-carbon atoms and heteroatoms, and specifically, the heteroatoms may include one or more atoms selected from the group consisting of O, N, Se, and S. The heterocycle may be monocyclic or polycyclic, and may be aromatic, aliphatic, or a condensed ring of aromatic and aliphatic, and may be selected from examples of the heteroaryl group or heterocyclic group except that it is not monovalent.

According to one embodiment of the present specification, in Chemical Formula 1, R and R 'are the same as or different from each other, and each independently a cyano group; Haloaryl group; Or a cyanoaryl group.

According to one embodiment of the present specification, in Chemical Formula 1, R and R 'are the same as or different from each other, and each independently a cyano group; Halophenyl group; Or a cyanophenyl group.

According to one embodiment of the present specification, in Chemical Formula 1, R and R 'are the same as or different from each other, and each independently a cyano group; Fluorophenyl group; Trifluorophenyl group or cyanophenyl group.

According to the exemplary embodiment of the present specification, in Chemical Formula 1, R1 to R4 are the same as or different from each other, and each independently hydrogen; Cyano group; Halogen group; Or a haloalkyl group.

According to the exemplary embodiment of the present specification, in Chemical Formula 1, R1 to R4 are the same as or different from each other, and each independently hydrogen; Cyano group; Fluoro groups; Or a trifluoromethyl group.

According to one embodiment of the present specification, in Chemical Formula 1, R1 to R4 are the same as or different from each other, and each independently represented by the following Chemical Formula A.

[Formula A]

In Chemical Formula A,

X3 is CH; CR5; Or N,

X4 is CH; CR6; Or N,

X5 is CH; CR7; Or N,

X6 is CH; CR8; Or N,

X7 is CH; CR9; Or N,

R5 to R9 are the same as or different from each other, and each independently deuterium; Halogen group; Cyano group; Alkyl groups; Haloalkyl group; Alkoxy groups; Or a haloalkoxy group,

는 상기 화학식 1에 연결되는 부위이다.

Is a site connected to the formula (1).

According to an exemplary embodiment of the present specification, in the formula A, R5 to R9 are the same as or different from each other, each independently a fluoro group; Cyano group; CH ₃ ; CF ₃ ; OCH ₃ ; Or OCF ₃ .

According to one embodiment of the present specification, in Chemical Formula 1, R1 to R4 are the same as or different from each other, and each independently selected from the following structural formulas.

In the above structural formula,

The definitions of R5 to R9 are the same as those of the formula (A).

는 상기 화학식 1에 연결되는 부위이다.

Is a site connected to the formula (1).

According to the exemplary embodiment of the present specification, in Chemical Formula 1, R1 to R4 are the same as or different from each other, and each independently selected from the following structural formulas.

는 상기 화학식 1에 연결되는 부위이다.In the above structural formula,

Is a site connected to the formula (1).

According to the exemplary embodiment of the present specification, in Chemical Formula 1, R1 to R4 are the same as or different from each other, and each independently selected from the following structural formulas.

는 상기 화학식 1에 연결되는 부위이다.In the above structural formula,

Is a site connected to the formula (1).

According to an exemplary embodiment of the present specification, in the general formula 1, at least one of R1 and R2 and R3 and R4 are bonded to each other to be substituted or unsubstituted aromatic ring; Or a substituted or unsubstituted heterocycle.

According to an exemplary embodiment of the present specification, in the general formula 1, at least one of R1 and R2 and R3 and R4 are bonded to each other to a cyano group, a halogen group or a haloalkyl group substituted or unsubstituted aromatic ring; Or it forms a heterocycle unsubstituted or substituted with a cyano group.

According to an exemplary embodiment of the present specification, in the formula 1, at least one of R1 and R2 and R3 and R4 are bonded to each other to form a ring represented by the following formulas a to e.

[Formula a]

[Formula b]

[Formula c]

[Formula d]

[Formula e]

In the formulas a to e,

Y1 is CR101 or N, Y2 is CR102 or N, Y3 is CR103 or N, Y4 is CR104 or N,

Z1 to Z4 are S or O,

G1 to G10 and R101 to R104 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; Cyano group; Or a haloalkyl group,

g1, g2, g4 and g7 to g10 are each 1 or 2,

g3 and g5 are each an integer from 1 to 3,

g6 is an integer from 1 to 6,

When each of g1 to g10 is a plurality, structures in a plurality of parentheses are the same or different from each other,

---- means a site that is bonded to the formula (1).

According to another exemplary embodiment of the present specification, G1 to G10 and R101 to R104 are the same as or different from each other, and each independently hydrogen; Fluoro groups; Or cyano group; Trifluoromethyl group.

According to the exemplary embodiment of the present specification, in Chemical Formula 1, at least one of R1 and R2 and R3 and R4 is one selected from the following structural formulas in combination with each other.

In the above structural formulas, ---- means a site bonded to the formula (1).

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

According to the exemplary embodiment of the present specification, the heterocyclic compound represented by Chemical Formula 1 may be prepared using materials and reaction conditions known in the art. For example, it may be prepared by referring to the synthesis method described in Scheme 1, literature [Macromolecules 2013, 46, 2141], or International Patent Publication No. 2015-067336, but is not limited thereto.

[Scheme 1]

In Reaction Scheme 1, the definitions of X1, X2 and R1 to R4 are the same as in Chemical Formula 1.

In addition, the present specification provides an organic light emitting device including the heterocyclic compound represented by Chemical Formula 1.

In one embodiment of the present specification, 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 layer of the organic material layer includes a heterocyclic compound represented by Chemical Formula 1 above. Provides

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 specification may have a structure including at least one layer of a hole injection layer, a hole buffer layer, a hole transport layer, an electron suppression layer, a hole suppression layer, an electron transport layer, and an electron injection layer in addition to the emission layer as an organic material layer. have. However, the structure of the organic light emitting device is not limited thereto, and may include a smaller number of organic layers.

According to an example, the organic light emitting device may be an organic light emitting device having a structure in which an anode, one or more organic material layers, and a cathode are sequentially stacked on a substrate (normal type). According to another example, the organic light emitting device may be an inverted type organic light emitting device in which a cathode, one or more organic material layers, and an anode are sequentially stacked on a substrate.

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

For example, the organic light emitting device of the present specification can be manufactured by sequentially laminating a first electrode, an organic material layer, and a second electrode on a substrate. At this time, a positive electrode is formed by depositing a metal or conductive metal oxide or an alloy thereof on a substrate using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation. And, after forming a hole injection layer, a hole transport layer, an organic material layer including a light emitting layer and an electron transport layer, it can be prepared by depositing a material that can be used as a cathode thereon. In addition to this method, an organic light emitting device may be formed by sequentially depositing a cathode material, an organic material layer, and a cathode material on a substrate.

In addition, the heterocyclic compound represented by Chemical Formula 1 may be formed as 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 means spin coating, dip coating, doctor blading, inkjet printing, screen printing, spraying, roll coating, and the like, but is not limited to these.

In addition to such a method, an organic light emitting device may be made by sequentially depositing an organic material layer and a cathode material from a cathode material on a substrate (International Patent Application Publication No. 2003/012890). However, the manufacturing method is not limited thereto.

In one embodiment of the present specification, the first electrode is an anode, and the second electrode is a cathode.

In another exemplary embodiment, the first electrode is a cathode, and the second electrode is an anode.

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

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

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

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

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

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

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

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

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

(9) Anode / hole injection layer / hole buffer layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode

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

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

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

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

(14) anode / hole transport layer / light emitting layer / hole suppression layer / electron transport layer / cathode

(15) Anode / hole transport layer / light emitting layer / hole suppression layer / electron transport layer / electron injection layer / cathode

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

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

For example, the structure of the organic light emitting device according to the exemplary embodiment of the present specification is illustrated in FIGS. 1 and 2.

FIG. 1 shows an example of an organic light emitting device comprising a substrate 1, an anode 2, a hole transport layer 6, a light emitting layer 3, and a cathode 4. In such a structure, the compound may be included in the hole transport layer.

2 shows an example of an organic light-emitting device comprising a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light emitting layer 3, an electron transport layer 8 and a cathode 4 It is done. In such a structure, the compound may be included in the hole injection layer or the hole transport layer.

The anode 2 is an electrode for injecting holes and may be any one of Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), or Zinc Oxide (ZnO). In addition, when the anode 2 is a reflective electrode, the anode 2 is a reflective layer made of any one of aluminum (Al), silver (Ag), or nickel (Ni) under a layer made of any one of ITO, IZO, or ZnO. It may further include.

The hole injection layer 5 may serve to facilitate injection of holes from the anode 2 to the light emitting layer 3. The hole injection layer 5 may include a heterocyclic compound represented by Chemical Formula 1 above. In this case, the hole injection layer 5 may be made of only the heterocyclic compound represented by Chemical Formula 1, but the heterocyclic compound represented by Chemical Formula 1 is mixed or doped with other hole injection layer materials known in the art. It can exist as a state. The heterocyclic compound represented by Chemical Formula 1 may occupy 100% of the hole injection layer, but may be doped at 0.1 to 50% by weight. The heterocyclic compound represented by Chemical Formula 1 is a derivative having an indenofluorene structure, and has excellent electron-accepting ability, thereby improving power consumption and lowering a driving voltage. The hole injection layer 5 may have a thickness of 1 to 150 nm. Here, when the thickness of the hole injection layer 5 is 1 nm or more, there is an advantage of preventing the hole injection characteristics from being deteriorated. If it is 150 nm or less, the hole injection layer 5 is too thick to move holes. In order to improve, there is an advantage that the driving voltage can be prevented from rising. As the other hole injection layer material, a hole injection material known in the art may be used. For example, in the group consisting of cupper phthalocyanine (CuPc), poly (3,4) -ethylenedioxythiophene (PEDOT), polyaniline (PANI), and NPD (N, N-dinaphthyl-N, N'-diphenyl benzidine) as the hole injection layer material. Any one or more selected may be used, but is not limited thereto.

The hole transport layer 6 may serve to facilitate the transport of holes. The hole transport layer 6 may include a heterocyclic compound represented by Chemical Formula 1 above. In this case, the hole transport layer 6 may be made of only the heterocyclic compound represented by Chemical Formula 1, but the heterocyclic compound represented by Chemical Formula 1 is mixed or doped with other hole transport layer materials known in the art. Can exist. The heterocyclic compound represented by Chemical Formula 1 may occupy 100% of the hole transport layer, but may be doped at 0.1 to 50% by weight. As the other hole transport layer material, a hole transport material known in the art may be used. For example, the hole transport layer 6 is NPD (N, N-dinaphthyl-N, N'-diphenylbenzidine), TPD (N, N'-bis- (3-methylphenyl) -N, N'-bis- (phenyl)- benzidine), s-TAD and MTDATA (4,4 ', 4 "-Tris (N-3-methylphenyl-N-phenyl-amino) -triphenylamine). For example, as a hole transport layer material, a triazole derivative, an oxadiazole derivative, an imidazole derivative, a polyaryl alkane derivative, a pyrazoline derivative and a pyrazolone derivative, a phenylenediamine derivative, an arylamine derivative, an amino substituted chalcone derivative, an oxa And sol derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, polysilane-based, aniline-based copolymers, and conductive polymer oligomers (especially thiophene oligomers).

A hole buffer layer may be additionally provided between the hole injection layer and the hole transport layer. The hole buffer layer may include a heterocyclic compound represented by Chemical Formula 1, and other hole injection or transport materials known in the art. Even when the hole buffer layer includes the heterocyclic compound represented by Chemical Formula 1, it may also consist of only the heterocyclic compound represented by Chemical Formula 1, but the heterocyclic compound represented by Chemical Formula 1 may be mixed or doped with other host materials. It can also be done in a state.

An electron suppressing layer may be provided between the hole transport layer and the light emitting layer, and a heterocyclic compound represented by Chemical Formula 1 or a material known in the art may be used.

The light emitting layer 3 may emit red, green and / or blue, and may be made of a phosphorescent material or a fluorescent material. As the light emitting layer material, those known in the art may be used. CBP (carbazole biphenyl) or mCP (1,3-bis (carbazol-9-yl)) may be used as the light emitting host material, but is not limited thereto.

When the light emitting layer 3 emits red light, PIQIr (acac) (bis (1-phenylisoquinoline) acetylacetonate iridium), PQIr (acac) (bis (1-phenylquinoline) acetylacetonate iridium), PQIr (tris (1) as the light emitting dopant Phosphorescent materials such as -phenylquinoline) iridium) and octaethylporphyrin platinum (PtOEP) or fluorescent materials such as Alq3 (tris (8-hydroxyquinolino) aluminum) can be used, but are not limited thereto. When the light emitting layer 3 emits green light, a phosphorescent material such as Ir (ppy) 3 (fac tris (2-phenylpyridine) iridium) or a fluorescent material such as Alq3 (tris (8-hydroxyquinolino) aluminum) is used as the light emitting dopant. This may be used, but is not limited to this. When the light emitting layer 3 emits blue light, a phosphorescent material such as (4,6-F ₂ ppy) ₂ Irpic is used as a light emitting dopant, but spiro-DPVBi, spiro-6P, distylbenzene (DSB), and disrylaryl Fluorescent materials such as Ren (DSA), PFO-based polymer, and PPV-based polymer may be used, but are not limited thereto.

A hole suppressing layer may be provided between the electron transport layer and the light emitting layer, and materials known in the art may be used.

The electron transport layer 8 may serve to facilitate the transport of electrons. Materials known in the art such as Alq3 (tris (8-hydroxyquinolino) aluminum), PBD, TAZ, spiro-PBD, BAlq, SAlq can be used. The electron transport layer 8 may have a thickness of 1 to 50 nm. Here, when the thickness of the electron transport layer 8 is 1 nm or more, there is an advantage of preventing the electron transport properties from deteriorating, and when it is 50 nm or less, the thickness of the electron transport layer 8 is too thick to improve the movement of electrons In order to prevent the driving voltage from rising, there is an advantage.

The electron injection layer may serve to facilitate injection of electrons. Alq3 (tris (8-hydroxyquinolino) aluminum), PBD, TAZ, spiro-PBD, BAlq or SAlq can be made of organic compounds or complexes or metal compounds known in the art. Metal compounds include metal halides, and storage can be used, for example, can be used LiQ, LiF, NaF, KF, RbF, CsF, FrF, BeF _2, MgF _2, CaF _2, SrF _2, BaF ₂ and RaF ₂ and the like. The thickness of the electron injection layer may be 1 to 50 nm. Here, when the thickness of the electron injection layer is 1 nm or more, there is an advantage of preventing the electron injection characteristics from being deteriorated, and when it is 50 nm or less, the thickness of the electron injection layer is too thick, so that the driving voltage is improved to improve electron movement There is an advantage that can be prevented from rising.

The cathode 4 is an electron injection electrode, and may be made of magnesium (Mg), calcium (Ca), aluminum (Al), silver (Ag), or an alloy thereof having a low work function. Here, the cathode 4 may be formed to have a thickness that is thin enough to transmit light when the organic light emitting device is a front or both sides light emitting structure, and reflect light when the organic light emitting device is a back light emitting structure. It can be formed to be thick enough.

According to another exemplary embodiment, the organic material layer includes two or more light emitting layers, and includes a charge generation layer including a heterocyclic compound represented by Chemical Formula 1 provided between the two light emitting layers. You can. In this case, one of the light emitting layers emits blue light, and the other emits yellow light to produce an organic light emitting device that emits white light. Between the light emitting layer and the anode or cathode, and between the light emitting layer and the charge generating layer, one or more organic material layers such as the hole injection layer, hole buffer layer, hole transport layer, electron suppression layer, hole suppression layer, electron transport layer, and electron injection layer are further described. Can be included. 3 includes a substrate 1, an anode 2 and a cathode 4, between the anode and the cathode, hole injection layers 5a, 5b, hole transport layers 6a, 6b, light emitting layers 3a, 3b And two units including the electron transport layers 8a and 8b, and showing an example of an organic light emitting device in which the charge generation layer 9 is provided between the units.

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

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

The preparation of the compound represented by Chemical Formula 1 and the organic light emitting device including the same will be described in detail in the following Examples. However, the following examples are intended to illustrate the present specification, and the scope of the present specification is not limited by them.

Preparation Example 1. Preparation of compound 16

1) Preparation of Intermediate A

1,2-bis (4- (trifluoromethyl) phenyl) ethane-1,2-dione 7.90g (22.8mmol) and 1,2,4,5-benzenetetraamine tetrahydrochloride salt 3.3g (11.6 mmol) was dissolved in 800 ml of acetic acid and stirred under reflux for 24 hours under nitrogen. After cooling, acetic acid was removed by distillation under reduced pressure, and after cooling, extraction was performed with water and dichloromethane, and further washed with distilled water, sodium carbonate solution, and brine solution. Next, dried and filtered over anhydrous sodium sulfate to obtain 5.3 g (60.0%) of intermediate a.

Next, 5.3 g (7.0 mmol) of the intermediate a obtained above was dissolved in 200 ml of chloroform, and 1.2 g (13.7 mmol) of sodium bicarbonate was added. The reaction solution was cooled to 0 ° C., and 2.2 g (14.0 mmol) of bromine was added dropwise, and 2.2 g of bromine and 1.2 g of sodium bicarbonate were added twice at 12 hour intervals. After completion of the reaction, 200 ml of 10% sodium thio sulfate (Na ₂ S2O ₃ ) solution was slowly added. Next, it was extracted with water and chloroform, dried over anhydrous sodium sulfate, and filtered. After distilling chloroform under reduced pressure, recrystallization with acetonitrile gave 3.20 g of intermediate A.

2) Preparation of compound 16

Under argon conditions, 1.1 g (12 mmol) of copper cyanide (CuCN) was added to 3.20 g (3.5 mmol) of intermediate A obtained above, and N-methyl-2-pyrrolidinone (20 mL) was added. And stirred. Thereafter, the mixture was heated to 180 ° C and stirred for 24 hours. After cooling to room temperature, 60 mL of ammonia water was added and stirred, and the resulting crystals were collected by filtration. The crystal collected by filtration was reslurried twice with 100 mL of water, and then reslurryed with 100 mL of ethanol. The obtained crystals were dried under reduced pressure with a vacuum dryer to obtain 1.0 g (1.2 mmol, 35%) of compound 16.

6 is a diagram showing the HPLC analysis data of the compound 16 prepared by Preparation Example 1, Figure 7 is a diagram showing the mass analysis data of the compound 16 prepared by Preparation Example 1. In Figure 7, the peak of Compound 16 was confirmed at M / Z = 808.

Preparation Example 2 Preparation of Compound 4

1) Preparation of Intermediate B

800 ml of 1,260 bis (4-fluorophenyl) ethane-1,2-dione 5.60g (22.8mmol) and 1,2,4,5-benzenetetraamine tetrahydrochloride salt 3.3g (11.6mmol) It was dissolved in acetic acid and stirred under reflux for 24 hours under nitrogen. After cooling, acetic acid was removed by distillation under reduced pressure, and after cooling, extraction was performed with water and dichloromethane, and further washed with distilled water, sodium carbonate solution, and brine solution. Next, dried and filtered over anhydrous sodium sulfate to obtain 4.4 g (68.0%) of intermediate b.

Next, 3.9 g (7.0 mmol) of the intermediate b obtained above was dissolved in 200 ml of chloroform, and 1.2 g of sodium bicarbonate (13.7 mmol) was added. The reaction solution was cooled to 0 ° C., and 2.2 g (14.0 mmol) of bromine was added dropwise, and 2.2 g of bromine and 1.2 g of sodium bicarbonate were added twice at 12 hour intervals. After completion of the reaction, 200 ml of 10% sodium thio sulfate (Na ₂ S2O ₃ ) solution was slowly added. Next, it was extracted with water and chloroform, dried over anhydrous sodium sulfate, and filtered. After distilling off chloroform under reduced pressure, it was recrystallized with acetonitrile to obtain 2.60 g of intermediate B.

2) Preparation of compound 4

In argon conditions, 2.50 g (3.5 mmol) of intermediate B obtained above was added with 1.1 g (12 mmol) of copper cyanide (CuCN) and N-methyl-2-pyrrolidinone (20 mL) was added. And stirred. Thereafter, the mixture was heated to 180 ° C and stirred for 24 hours. After cooling to room temperature, 60 mL of ammonia water was added and stirred, and the resulting crystals were collected by filtration. The crystal collected by filtration was reslurried twice with 100 mL of water, and then reslurryed with 100 mL of ethanol. The obtained crystals were dried under reduced pressure with a vacuum dryer to obtain 0.8 g (1.2 mmol, 38%) of Compound 4. 4 is a diagram showing the HPLC analysis data of the compound 4 prepared by Preparation Example 2, Figure 5 is a diagram showing the mass analysis data of the compound 4 prepared by Preparation Example 2. In Figure 7, the peak of Compound 4 was confirmed at M / Z = 608.

Example 1

The ITO (indium tin oxide) glass was patterned to have a light emitting area of 3 mm × 3 mm and then washed. After the substrate was mounted in the vacuum chamber, the basic pressure was 1 × 10 ^-6 torr, and then HT-1 was formed as a hole injection layer on the positive electrode ITO to a thickness of 100 MPa, but Compound 16 was added at a doping concentration of 25% by weight. Doped. Subsequently, HT-1 was formed to a thickness of 600 Å as a hole transport layer, and a dopant BD-A was deposited to the host MADN as a light emitting layer to have a weight ratio of 40: 2, and Alq ₃ was formed as a thickness of 300 으로 as an electron transport layer. LiF was formed as an electron injection layer to a thickness of 10 Pa, and Al was sequentially formed to a thickness of 800 Pa as a cathode to fabricate an organic light emitting device.

Example 2

An organic light-emitting device was manufactured in the same manner as in Example 1, except that Compound 4 was used instead of Compound 16.

Comparative Example 1

An organic light emitting device was manufactured in the same manner as in Example 1, except that Compound HAT-CN was used instead of Compound 16.

Comparative Example 2

An organic light emitting device was manufactured in the same manner as in Example 1, except that Compound 16 was not used.

The driving voltage, current density, current efficiency, power efficiency, and luminance of the organic light emitting devices manufactured in Examples 1 and 2 and Comparative Examples 1 and 2 were measured and are shown in Table 1 below.

Hole injection layer
Doping material Driving voltage
(V) Current density
(mA / cm ² ) Current efficiency
(cd / A) Power efficiency
(lm / W) Luminance
(cd / m ² ) Example 1 Compound 16 4.42 10 60.04 42.674 6004 Example 2 Compound 4 4.71 10 54.09 36.078 5409 Comparative Example 1 HAT-CN 5.8 10 50.08 27.126 5008 Comparative Example 2 - 6.8 10 47.86 22.111 4786

In Table 1, the organic light emitting device using the heterocyclic compound represented by Formula 1 according to an exemplary embodiment of the present specification as a doping material of the hole injection layer, compared to the organic light emitting device of Comparative Examples 1 and 2, the driving voltage is It was found that the current efficiency, power efficiency and luminance were high.

8 is a view showing current densities according to driving voltages of Examples 1, 2 and Comparative Example 1 according to an exemplary embodiment of the present specification, and in Examples 8, Examples 1 and 2 are compared with Comparative Example 1 and driven. It can be seen that the voltage is low and the efficiency is excellent.

1: Substrate
2: anode
3, 3a, 3b: light emitting layer
4: Cathode
5, 5a, 5b: hole injection layer
6, 6a, 6b: hole transport layer
8, 8a, 8b: electron transport layer

Claims (12)

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

In Chemical Formula 1,
X1 is N or CR,
X2 is N or CR ',
However, X1 and X2 are not N at the same time,
R and R 'are the same as or different from each other, and each independently a cyano group; Haloaryl group; Or a cyanoaryl group,
R1 to R4 are the same as or different from each other, and each independently hydrogen; Halogen group; Cyano group; Haloalkyl group; Or an aromatic ring represented by the following formula (A), at least one of R1 and R2 and R3 and R4 are bonded to each other and unsubstituted or substituted with a cyano group, a halogen group, or a haloalkyl group; Or it may form a heterocycle unsubstituted or substituted with a cyano group,
[Formula A]

In Chemical Formula A,
X3 is CH; CR5; Or N,
X4 is CH; CR6; Or N,
X5 is CH; CR7; Or N,
X6 is CH; CR8; Or N,
X7 is CH; CR9; Or N,
R5 to R9 are the same as or different from each other, and each independently deuterium; Halogen group; Cyano group; Alkyl groups; Haloalkyl group; Alkoxy groups; Or a haloalkoxy group,

Is a site connected to the formula (1). delete delete The method according to claim 1, wherein R1 to R4 are the same as or different from each other, and each independently a heterocyclic compound that is any one selected from the following structural formula:

In the above structural formula,
R5 to R9 are the same as or different from each other, and each independently deuterium; Halogen group; Cyano group; Alkyl groups; Haloalkyl group; Alkoxy groups; Or a haloalkoxy group,

Is a site connected to the formula (1). The method according to claim 1, wherein R1 to R4 are the same as or different from each other, and each independently a heterocyclic compound that is any one selected from the following structural formula:

In the above structural formula,

Is a site connected to the formula (1). delete The method according to claim 1, wherein Formula 1 is a heterocyclic compound represented by 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 at least one layer of the organic material layer is a heterocycle according to any one of claims 1, 4, 5 and 7. Organic light emitting device comprising a compound. The method according to claim 8, The organic material layer includes one of a hole injection layer, a hole buffer layer, a hole transport layer and an electron suppression layer, and the hole injection layer, hole buffer layer, hole transport layer or electron suppression layer will contain the heterocyclic compound Organic light emitting device. The method according to claim 9, The hole injection layer, the hole buffer layer, the hole transport layer or the electron suppressing layer is an organic light-emitting device consisting only of the heterocyclic compound. The method according to claim 9, The hole injection layer, the hole buffer layer, the hole transport layer or the electron suppressing layer is an organic light-emitting device comprising the heterocyclic compound in an amount of 0.1 to 50% by weight based on the weight of each layer. The method according to claim 8, wherein the organic layer includes at least two light-emitting layers, and the organic layer further comprises a charge generation layer (charge generation layer) comprising the heterocyclic compound of Formula 1 provided between the light-emitting layer of the two layers Light emitting element.

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