KR102209930B1 - Spiro compound and organic light emitting device comprising the same - Google Patents

Abstract

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

Description

Spiro compound and an organic light emitting device comprising the same TECHNICAL FIELD [Spiro Compound and Organic Light Emitting Device Comprising

This specification claims the benefit of the filing date of Korean Patent Application No. 10-2018-0021868 filed with the Korean Intellectual Property Office on February 23, 2018, the entire contents of which are incorporated herein.

The present specification relates to a spiro compound and an organic light emitting device formed using a spiro compound.

In general, the organic light emission phenomenon refers to a phenomenon in which electrical energy is converted into light energy using organic materials. An organic light emitting device using the organic light emitting phenomenon has a structure including an anode, a cathode, and an organic material layer therebetween. Here, the organic material layer is often made of a multi-layered structure composed of different materials in order to increase the efficiency and stability of the organic light emitting device.For example, it 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. In the structure of such an organic light-emitting device, when a voltage is applied between the two electrodes, holes are injected from the anode and electrons from the cathode are injected into the organic material layer, and excitons are formed when the injected holes and electrons meet. It glows when it falls back to the ground.

Development of a new material for the organic light emitting device as described above is continuously required.

US Patent Application Publication No. 2004-0251816

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

According to an exemplary embodiment of the present specification, a spiro compound represented by the following Chemical Formula 1 was provided.

[Formula 1]

[Formula 2]

[Formula 3]

R1 is a substituent represented by Formula 2 or 3,

In Formulas 1 to 3,

R2 to R6 are the same as or different from each other, and each independently hydrogen, deuterium, nitrile group, halogen group, substituted or unsubstituted alkyl group, substituted or unsubstituted silyl group, substituted or unsubstituted amine group, substituted or unsubstituted A substituted aryl group, or a substituted or unsubstituted heteroaryl group, or adjacent substituents may be bonded to each other to form a substituted or unsubstituted ring,

L is a direct bond; A substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,

a, b and f are each an integer of 0 to 7,

c is an integer from 0 to 3,

When c is 0, L is a substituted or unsubstituted heteroarylene group,

d is an integer from 0 to 8,

e is an integer from 0 to 3,

When a is plural, R2 is the same as or different from each other,

When b is plural, R3 is the same as or different from each other,

When d is plural, R4 is the same as or different from each other,

When e is plural, R5 is the same as or different from each other,

When f is plural, R6 is the same as or different from each other.

In addition, the present specification is a first electrode; A second electrode provided opposite to the first electrode; And one or two or more organic material layers provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes the spiro compound.

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

In particular, by fixing the substituent at the 4,4' position, the triplet energy can be increased, and a P-type and N-type substituent can be introduced at each substitution position to be applied as a bipolar host.

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

Hereinafter, the present specification has been described in more detail.

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

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

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

The term "substituted" means that the hydrogen atom bonded to the carbon atom of the 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, the position where the substituent can be substituted, and when two or more are substituted , Two or more substituents may be the same or different from each other.

In the present specification, the term "substituted or unsubstituted" refers to deuterium; Nitrile group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted aryl group; A substituted or unsubstituted amine group; And a substituted or unsubstituted heterocyclic group substituted with one or two or more substituents selected from the group consisting of, or two or more of the substituents exemplified above are substituted with a connected substituent, or have no substituent. For example, the "substituent to which two or more substituents are connected" may be an aryl group substituted with an aryl group, an aryl group substituted with a heteroaryl group, a heterocyclic group substituted with an aryl group, an aryl group substituted with an alkyl group, and the like.

In the present specification, the halogen group may be a fluoro group, a chloro group, a bromo group, or an iodo group.

In the present specification, the alkyl group may be a linear or branched chain, 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, but are not limited thereto.

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 silyl group is specifically trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, phenylsilyl group, etc. However, it is not limited thereto.

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 it is preferably 6 to 30 carbon atoms. Specifically, the monocyclic aryl group may be a phenyl group, a biphenyl group, or a terphenyl group, but is not limited thereto.

When the aryl group is a polycyclic aryl group, the number of carbon atoms is not particularly limited. It is preferable that it has 10 to 30 carbon atoms. Specifically, the polycyclic aryl group may be a naphthyl group, an anthracenyl group, a phenanthryl group, a triphenyl group, a pyrenyl group, a phenalenyl group, a perylenyl group, a chrysenyl group, a fluorenyl group, and the like, but are limited thereto. no.

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

,

,

,

,

및

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

,

,

,

,

And

Etc. However, it is not limited thereto.

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

In the present specification, the heteroaryl group includes one or more atoms and heteroatoms other than carbon, and specifically, the heteroatom may include one or more atoms selected from the group consisting of O, N, Se, and S. The number of carbon atoms is not particularly limited, but is preferably 2 to 30 carbon atoms, and the heteroaryl group may be monocyclic or polycyclic. Examples of the heterocyclic group include thiophene group, furanyl group, pyrrole group, imidazolyl group, thiazolyl group, oxazolyl group, oxadiazolyl group, pyridyl group, bipyridyl group, pyrimidyl group, triazinyl group, tria Zolyl group, acridyl group, pyridazinyl group, pyrazinyl group, quinolinyl group, quinazolinyl group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group , Isoquinolinyl group, indolyl group, carbazolyl group, benzoxazolyl group, benzimidazolyl group, benzothiazolyl group, benzocarbazolyl group, benzothiophene group, dibenzothiophene group, benzofuranyl group, p Nanthrolinyl group (phenanthroline), isoxazolyl group, thiadiazolyl group, phenothiazinyl group, dibenzofuranyl group, and the like, but are not limited thereto.

In the present specification, examples of the heteroarylamine group include a substituted or unsubstituted monoheteroarylamine group, a substituted or unsubstituted diheteroarylamine group, or a substituted or unsubstituted triheteroarylamine group. The heteroarylamine group including two or more heteroaryl groups may include a monocyclic heteroaryl group, a polycyclic heteroaryl group, or a monocyclic heteroaryl group and a polycyclic heteroaryl group at the same time. For example, the heteroaryl group in the heteroarylamine group may be selected from the examples of the heteroaryl group described above.

In the present specification, examples of the heteroaryl group in the N-arylheteroarylamine group and the N-alkylheteroarylamine group are the same as those of the aforementioned heteroaryl group.

In the present specification, the arylene group is the same as the definition of the aryl group, except that it is divalent.

In the present specification, the heteroarylene group is the same as the definition of the heteroaryl group, except that it is divalent.

According to an exemplary embodiment of the present specification, Chemical Formula 2 is represented by any one of the following Chemical Formulas 4 to 6.

[Formula 4]

[Formula 5]

[Formula 6]

In Formulas 4 to 6, R4 is as defined in Formula 1,

R7 to R9 are the same as or different from each other, and each independently hydrogen, deuterium, nitrile group, halogen group, substituted or unsubstituted alkyl group, substituted or unsubstituted silyl group, substituted or unsubstituted amine group, substituted or unsubstituted A substituted aryl group, or a substituted or unsubstituted heteroaryl group,

Ar1 and Ar2 are the same as or different from each other, and each independently hydrogen, deuterium, nitrile group, halogen group, substituted or unsubstituted alkyl group, substituted or unsubstituted silyl group, substituted or unsubstituted amine group, substituted or unsubstituted A substituted aryl group, or a substituted or unsubstituted heteroaryl group,

d is an integer from 0 to 7,

g is an integer from 0 to 8,

h is an integer from 0 to 7,

i is an integer from 0 to 10,

When g is plural, R7 is the same as or different from each other,

When h is plural, R8 is the same as or different from each other,

When i is plural, R9 is the same as or different from each other.

In an exemplary embodiment of the present specification, Formula 1 is represented by any one of the following Formulas 7 to 9.

[Formula 7]

[Formula 8]

[Formula 9]

In Formulas 7 to 9, R2 to R6 and a to f are as defined in Formulas 1 to 3,

R9 is hydrogen, deuterium, nitrile group, halogen group, substituted or unsubstituted alkyl group, substituted or unsubstituted silyl group, substituted or unsubstituted amine group, substituted or unsubstituted aryl group, or substituted or unsubstituted hetero Is an aryl group,

Ar3 is hydrogen, deuterium, a nitrile group, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted amine group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted hetero Is an aryl group,

i is an integer from 0 to 10, and when i is plural, R9 is the same as or different from each other.

According to an exemplary embodiment of the present specification, L is a direct bond, a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, or a substituted or unsubstituted heteroarylene group having 3 to 20 carbon atoms.

According to an exemplary embodiment of the present specification, L is a direct bond, an arylene group having 6 to 20 carbon atoms, or a heteroarylene group containing N, O, or S having 3 to 20 carbon atoms.

According to an exemplary embodiment of the present specification, L is a direct bond, a monocyclic arylene group having 6 to 20 carbon atoms, a polycyclic arylene group having 10 to 20 carbon atoms, or N, O, or S containing 3 to 20 carbon atoms. It is a heteroarylene group.

According to an exemplary embodiment of the present specification, L is a direct bond, a monocyclic arylene group having 6 to 20 carbon atoms, a polycyclic arylene group having 10 to 20 carbon atoms, or N, O, or S containing 3 to 20 carbon atoms. It is a heteroarylene group.

According to an exemplary embodiment of the present specification, L is a direct bond, a divalent phenyl group, a divalent biphenyl group, a divalent terphenyl group, a divalent naphthyl group, a divalent fluorene group, a divalent carbazole group, a divalent triazine group, It is a divalent pyrimidine group, a divalent pyridine group, a divalent dibenzothiophene group, or a divalent dibenzofuran group.

According to an exemplary embodiment of the present specification, L is a direct bond, a divalent phenyl group, or a divalent dibenzofuran group.

According to an exemplary embodiment of the present specification, when c is 0, L is a substituted dibenzofuran group.

According to an exemplary embodiment of the present specification, when c is 0, L is an unsubstituted dibenzofuran group.

According to an exemplary embodiment of the present specification, R2 to R6, and R9 are the same as or different from each other, and each independently hydrogen, deuterium, a nitrile group, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted silyl group , A substituted or unsubstituted amine group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, or adjacent substituents may be bonded to each other to form a substituted or unsubstituted ring.

According to an exemplary embodiment of the present specification, R2 to R6, and R9 are the same as or different from each other, and each independently hydrogen; Nitrile group; Halogen group; An alkyl group having 1 to 10 carbon atoms; A silyl group unsubstituted or substituted with an alkyl group having 1 to 10 carbon atoms; An alkoxy group having 1 to 10 carbon atoms; Aryl group having 6 to 20 carbon atoms; Or a substituted or unsubstituted N, O, or S-containing heteroaryl group having 3 to 10 carbon atoms.

According to an exemplary embodiment of the present specification, R2 to R6, and R9 are the same as or different from each other, and each independently hydrogen; Nitrile group; Halogen group; An alkyl group having 1 to 10 carbon atoms; A silyl group unsubstituted or substituted with an alkyl group having 1 to 10 carbon atoms; An alkoxy group having 1 to 10 carbon atoms; Aryl group having 6 to 20 carbon atoms; Or an N, O, or S-containing heteroaryl group having 3 to 10 carbon atoms unsubstituted or substituted with an aryl group having 6 to 20 carbon atoms.

According to an exemplary embodiment of the present specification, R2 to R6, and R9 are the same as or different from each other, and each independently hydrogen; Nitrile group; F; Cl; Br; I; Methyl group; Ethyl group; Propyl group; Isopropyl group; Butyl group; Terbutyl group; Pentyl group; Hexyl group; Heptyl group; Octyl group; Nonyl group; Decyl group; A silyl group unsubstituted or substituted with a methyl group; Methoxy group; Ethoxy group; Propoxy group; Butoxy group; Terbutoxy group; Pentoxy group; Phenyl group; Biphenyl group; Terphenyl group; Naphthyl group; Anthracene group; Phenanthrene group; A pyridine group unsubstituted or substituted with a phenyl group, a naphthyl group, or a biphenyl group; A pyrimidine group unsubstituted or substituted with a phenyl group, a naphthyl group, or a biphenyl group; A triazine group unsubstituted or substituted with a phenyl group, a naphthyl group, or a biphenyl group; A carbazole group unsubstituted or substituted with a phenyl group, a naphthyl group, or a biphenyl group; A dibenzofuran group unsubstituted or substituted with a phenyl group, a naphthyl group, or a biphenyl group; Or a phenyl group, a naphthyl group, or a dibenzothiophene group unsubstituted or substituted with a biphenyl group.

According to an exemplary embodiment of the present specification, R2 to R6, and R9 are the same as or different from each other, and each independently hydrogen; Or a phenyl group, a naphthyl group, or a carbazole group unsubstituted or substituted with a biphenyl group.

According to an exemplary embodiment of the present specification, Ar1 to Ar3 are the same as or different from each other, and each independently a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group.

According to an exemplary embodiment of the present specification, Ar1 to Ar3 are the same as or different from each other, and each independently a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a substituted or unsubstituted N, O, or S containing It is a C3-C20 heteroaryl group.

According to the exemplary embodiment of the present specification, Ar1 to Ar3 are the same as or different from each other, and each independently a monocyclic aryl group having 6 to 20 carbon atoms, or a polycyclic aryl group having 10 to 20 carbon atoms.

According to an exemplary embodiment of the present specification, Ar1 to Ar3 are the same as or different from each other, and each independently a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, an anthracene group, a phenanthrene group, and a fluorene group. It is a pyrene group or a triphenylene group.

According to an exemplary embodiment of the present specification, Ar1 to Ar3 are the same as or different from each other, and each independently a phenyl group, a biphenyl group, or a naphthyl group.

According to another exemplary embodiment of the present specification, the spiro compound of Formula 1 may be represented by the following structural formulas.

In addition, the present specification is a first electrode; A second electrode provided opposite to the first electrode; And one or two or more organic material layers provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes the spiro compound.

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

The organic material layer of the organic light emitting device of the present invention may have a single-layer structure, but may have a multilayer 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, a light emitting layer, an electron transport layer, an electron injection layer, and the like as an organic material layer. However, the structure of the organic light-emitting device is not limited thereto, and may include a smaller number of organic material layers. In addition, the organic material layer may include at least one of an electron transport layer, an electron injection layer, and a layer that simultaneously transports electrons and injects electrons, and at least one of the layers may include the compound.

For example, the structure of the organic light-emitting device of the present invention may have a structure as shown in FIG. 1, but is not limited thereto.

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

FIG. 2 illustrates a structure of an organic light emitting diode in which a first electrode 2, a light emitting layer 5, and a second electrode 4 are sequentially stacked on a substrate 1. In FIG. 2, an organic material layer may be added between the first electrode and the emission layer, and between the emission layer and the second electrode. Examples of the organic material layer that may be added include, but are not limited to, a hole injection layer, a hole transport layer, a hole injection and transport layer, an electron blocking layer, a hole blocking layer, an electron transport layer, and an electron injection layer.

1 and 2 illustrate an organic light emitting device and are not limited thereto.

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

In an exemplary embodiment of the present invention, the organic material layer including the spiro compound of Formula 1 includes an emission layer, and the spiro compound of Formula 1 as a host of the emission layer.

In an exemplary embodiment of the present invention, at least one compound having a gap (ΔE _st ) of ≤0.2 eV between the lowest triplet state T1 and the first excited singlet state S1 is included as a dopant of the emission layer.

In measuring the ΔE _st , the UV-vis absorption spectrum was measured using JASCO's V-730, and the photoluminescence spectrum in the film deposition state and the photoluminescence spectrum in the low-temperature state were Perkin Elmer. was measured using a LS-55's, as measured when the solvent content in 1Х10- ⁵ M of compound 1, using HPLC grade THF, was measured in liquid nitrogen.

In an exemplary embodiment of the present invention, the organic material layer includes an emission layer, and the emission layer includes a host and a dopant in a weight ratio of 1:99 to 50:50.

In an exemplary embodiment of the present invention, the organic material layer includes an emission layer, and an organic compound or a metal complex compound is included in the emission layer as a dopant.

In an exemplary embodiment of the present invention, the emission layer includes a phosphorescent dopant.

In one embodiment of the present invention, the light emitting layer includes a phosphorescent host.

In one embodiment of the present invention, the organic material layer includes an emission layer, and the emission layer includes the spiro compound of Formula 1 as a phosphorescent host of the emission layer.

In an exemplary embodiment of the present invention, the light emitting layer includes an iridium-based complex as a dopant.

In an exemplary embodiment of the present invention, the organic material layer includes an emission layer, and the emission layer includes any one of the following compounds as a dopant.

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

As the anode material, a material having a large work function is preferable so that holes can be smoothly injected into the organic material layer. Specific examples of the cathode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); A combination of a metal and an oxide such as ZnO:Al or SnO ₂ :Sb; Poly(3-methyl compound), poly[3,4-(ethylene-1,2-dioxy) compound] (PEDT), conductive polymers such as polypyrrole and polyaniline, but are not limited thereto.

It is preferable that the cathode material is 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; There are multi-layered materials such as LiF/Al or LiO ₂ /Al, but are not limited thereto.

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

The hole transport material is a material capable of transporting holes from an anode or a hole injection layer and transferring them to the emission layer, and a material having high mobility for holes is suitable. Specific examples include an arylamine-based organic material, a conductive polymer, and a block copolymer including a conjugated portion and a non-conjugated portion, but are not limited thereto.

The light-emitting material is a material capable of emitting light in a visible light region by transporting and bonding 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 compound; Benzoxazole, benzthiazole, and benzimidazole-based compounds; Poly(p-phenylenevinylene) (PPV)-based polymer; Spiro compounds; Polyfluorene, rubrene, and the like, but are not limited thereto.

The emission layer may include a host material and a dopant material. Host materials include condensed aromatic ring derivatives or heterocyclic-containing compounds. Specifically, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, and fluoranthene compounds, and heterocycle-containing compounds include spiro compounds, dibenzofuran derivatives, and ladder furan Compounds, pyrimidine derivatives, and the like, but are not limited thereto.

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

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

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

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

Specifically, in the exemplary embodiment of the present specification, the step of preparing a substrate; Forming a cathode or an anode on the substrate; Forming one or more organic material layers on the cathode or anode; And forming an anode or a cathode on the organic material layer, wherein at least one layer of the organic material layer is formed using the spiro compound.

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

In the organic light-emitting device according to the present specification, all compounds described in the specification may be synthesized by different types of substituents in the following Preparation Examples.

<General Manufacturing Example>

Synthesis of C

In a nitrogen atmosphere, 20 mmol of Sm A, 22 mmol of Sm B, and 2 mol% of tetrakis triphenylphosphine palladium (Tetrakis (triphenylphosphine) palladium) were added to 60 ml of tetrahydrofuran, and 60 mmol of potassium carbonate were dissolved in 30 ml of water and mixed. After stirring at 80 °C for 12 hours, the reaction was terminated, cooled to room temperature, and water and an organic layer were separated. Taking only the organic layer, anhydrous magnesium sulfate was added and stirred. After filtration with a silica pad (silica pad), the solution was concentrated under reduced pressure, followed by column purification, and intermediate C was obtained in a 75% yield.

Synthesis of F

After completely dissolving 20 mmol of intermediate C and 20 mmol of Sm D in 60 ml of toluene under a nitrogen atmosphere, 24 mmol of sodium-tert-butoxide was added and stirred while increasing the temperature until reflux. When reflux started, 1 mol% of bis(tri-tert-butylphosphine)palladium was slowly dropped and added. After 6 hours, the reaction was terminated, the temperature was lowered to room temperature, concentrated under reduced pressure, and purified by column to obtain Compound F in 65% yield.

Synthesis of G

In a nitrogen atmosphere, 20 mmol of intermediate C, 22 mmol of Sm E and 1 mol% of bis (tri-t-butyl phosphine) palladium (BIs (tri-tert-butyl phosphine) palladium) were added to 60 ml of tetrahydrofuran, and 60 mmol of potassium carbonate was added to 30 ml of water. Melted and mixed. After stirring at 80 °C for 12 hours, the reaction was terminated, cooled to room temperature, and water and an organic layer were separated. Taking only the organic layer, anhydrous magnesium sulfate was added and stirred. After filtration with a silica pad (silica pad), the solution was concentrated under reduced pressure, followed by column purification, and Compound G was obtained in 73% yield.

Preparation Example of Compound 1

The compound 4-bromo-4'-chloro-9,9'-spirobifluorene (10.0g, 23.36mmol) and 9H-carbazole (3.9g, 23.36mmol) were completely dissolved in 70ml of xylene under a nitrogen atmosphere. Then, potassium hydroxide (2.6g, 46.72mmol) and 1,10-phenanthroline (6.7g, 37.38mmol) were added and stirred while raising the temperature until reflux. When reflux started, copper iodide (0.45g, 2.34mmol) was added in a solid state several times. After 8 hours, the reaction was completed, the temperature was lowered to room temperature, filtered with silica, concentrated under reduced pressure, and purified by column to prepare Intermediate 1-1 (8.18g, 68% yield).

MS[M+H] ⁺ = 516

The intermediate 1-1 (8.18g, 15.88mmol), (3-cyanophenyl) boronic acid (2.57g, 17.47mmol) and bis (tri-t-butylphosphine) palladium (BIs (tri-tert) under nitrogen atmosphere -butylphosphine)palladium) (0.08g, 0.16mmol) was added to 45ml of tetrahydrofuran, and potassium carbonate (6.6g, 47.64mmol) was dissolved in 20ml of water and mixed. After stirring at 80 °C for 12 hours, the reaction was terminated, cooled to room temperature, and water and an organic layer were separated. Taking only the organic layer, anhydrous magnesium sulfate was added and stirred. After filtration with a silica pad (silica pad), the solution was concentrated under reduced pressure, followed by column purification, to give compound 1 (6.56g, 71% yield).

MS: [M+H]+= 583.

Preparation example of compound 2

Except for using Intermediate 1-1 (10.0g, 21.35mmol) and dibenzo[b,d]furan-4-ylboronic acid (4.5g, 21.35mmol), the compound was reacted and purified in the same manner as in the synthesis of Compound 1 above. 2 (9.17 g, 73% yield) was obtained.

MS: [M+H]+= 648

Preparation Example of Compound 3

Intermediate 1-1 (10.0g, 21.35mmol) and 6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)dibenzo[b,d]furan Except for using -2-carbonitrile (6.8g, 21.35mmol), it was reacted and purified in the same manner as in the synthesis of compound 1 to obtain compound 3 (10.44g, 80% yield).

MS: [M+H]+= 673

Preparation example of compound 4

Intermediate 1- above except that 4-bromo-4'-chloro-9,9'-spirobifluorene (10.0g, 23.36mmol) and 2-phenyl-9H-carbazole (5.68g, 23.36mmol) were used. Reaction was carried out in the same manner as in synthesis of 1, followed by purification to obtain intermediate 4-1 (9.1 g, 66% yield).

MS: [M+H]+= 592

Intermediate 4-1 (9.1g, 15.39mmol) and (3,5-dithianophenyl) boronic acid (2.9g, 16.93mmol) were reacted and purified in the same manner as in the synthesis of Compound 1, except that Compound 4 (7.15g, 68% yield) was obtained.

MS: [M+H]+= 684

Of compound 5 Manufacturing example

4-Bromo-4'-chloro-9,9'-spirobifluorene (10.0g, 23.36mmol) and 5-phenyl-5,12-dihydroindolo[3,2-a]carbazole (7.8 g, 23.36mmol) was reacted and purified in the same manner as in the synthesis of Intermediate 1-1, to obtain Intermediate 5-1 (9.7g, 61% yield).

MS: [M+H]+= 681

Except for using Intermediate 5-1 (9.7g, 14.25mmol) and dibenzo[b,d]furan-2-ylboronic acid (3.3g, 15.67mmol), the compound was reacted and purified in the same manner as in the synthesis of Compound 1 above. 5 (8.2g, 71% yield) was obtained.

MS: [M+H]+= 813

Preparation example of compound 6

.

In a nitrogen atmosphere, 4-bromo-4'-chloro-9,9'-spirobifluorene (10.0g, 23.36mmol) and zinc cyanide (1.65g, 14.02mmol) were added to 60ml of dimethylformamide, and the temperature was raised to increase the temperature. Stirred. When reflux begins, tetrakis triphenylphosphine palladium (2.7g, 2.33mmol) was added in batches, the reaction was terminated after 3 hours, the temperature was lowered to room temperature, filtered through silica, concentrated under reduced pressure, and then purified by column. Thus, intermediate 6-1 (6.13g, 70% yield) was prepared.

MS[M+H] ⁺ = 376

In a nitrogen atmosphere, intermediate 6-1 (6.13g, 16.34mmol), 9H-carbazole (2.7g, 16.34mmol), and sodium t-butoxide (1.9g, 19.61mmol) were added to 45ml of xylene, and the temperature was raised and stirred. I did. When reflux started, bis (tri-tert-butylphosphine) palladium (BIs (tri-tert-butylphosphine) palladium) (0.08g, 0.16mmol) was dissolved in xylene and slowly dropped and added dropwise. After 5 hours, the reaction was completed, the temperature was lowered to room temperature, filtered through silica, concentrated under reduced pressure, and purified by column to prepare compound 6 (5.0g, 61% yield).

MS[M+H] ⁺ = 507

Preparation example of compound 7

Synthesis of Compound 6 except for using Intermediate 6-1 (6.13g, 16.34mmol) and 5-phenyl-5,8-dihydroindolo[2,3-c]carbazole (5.4g, 16.34mmol) Reaction and purification were performed in the same manner to obtain compound 7 (6.9g, 63% yield).

MS: [M+H]+= 672

Preparation Example of Compound 8

In a nitrogen atmosphere, 4-bromo-4'-chloro-9,9'-spirobifluorene (10g, 23.36mmol), indolo[3,2,1-jk]carbazol-10-yl boronic acid (7.3 g, 25.69mmol) and tetrakis triphenylphosphine palladium (0.5g, 0.47mmol) were added to 75ml of tetrahydrofuran, and potassium carbonate (9.7g, 70.08mmol) was dissolved in 30ml of water and mixed. . After stirring at 80 °C for 12 hours, the reaction was terminated, cooled to room temperature, and water and an organic layer were separated. Taking only the organic layer, anhydrous magnesium sulfate was added and stirred. After filtration with a silica pad (silica pad), the solution was concentrated under reduced pressure, followed by column purification, and intermediate 8-1 (10.0 g, 73%) was obtained.

MS: [M+H]+= 590

Intermediate 8-1 (10.0g, 17.05mmol) and (2-cyanophenyl) boronic acid (2.8g, 18.76mmol) were reacted and purified in the same manner as in the synthesis of compound 1, except that compound 8 (7.2g , 64% yield) was obtained.

MS: [M+H]+= 657

<Example>

A glass substrate coated with a thin film of ITO (ndium tin oxide) having a thickness of 1,000Å was placed in distilled water dissolved in a detergent and washed with ultrasonic waves. In this case, Fischer Co. product was used as a detergent, and distilled water secondarily filtered with a filter made by Millipore Co. was used as distilled water. After washing the ITO for 30 minutes, it was repeated twice with distilled water to perform ultrasonic cleaning for 10 minutes. After washing with distilled water, ultrasonic cleaning was performed with a solvent of isopropyl alcohol, acetone, and methanol, dried, and then transported to a plasma cleaner. In addition, after cleaning the substrate for 5 minutes using oxygen plasma, the substrate was transported to a vacuum evaporator.

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

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

<Experimental Example 1-2>

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

<Experimental Example 1-3>

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

<Experimental Example 1-4>

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

<Experimental Example 1-5>

An organic light-emitting device was manufactured in the same manner as in Experimental Example 1-1, except that Compound 5 was used instead of Compound 1 in Experimental Example 1-1.

<Experimental Example 1-6>

An organic light-emitting device was manufactured in the same manner as in Experimental Example 1-1, except that Compound 6 was used instead of Compound 1 in Experimental Example 1-1.

<Experimental Example 1-7>

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

<Experimental Example 1-8>

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

<Comparative Example 1-1>

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

<Comparative Example 1-2>

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

<Comparative Example 1-3>

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

When an electric current was applied to the organic light-emitting devices manufactured according to Experimental Examples 1-1 to 1-8 and Comparative Examples 1-1 and 1-3, the results of Table 1 were obtained.

compound
(Host) Voltage
(V@10mA/cm ² ) efficiency
(cd/A@10mA/cm ² ) EL peak
(nm) Experimental Example 1-1 Compound 1 3.63 44.93 517 Experimental Example 1-2 Compound 2 3.86 42.64 516 Experimental Example 1-3 Compound 3 3.85 43.62 518 Experimental Example 1-4 Compound 4 3.75 42.75 517 Experimental Example 1-5 Compound 5 3.88 42.51 515 Experimental Example 1-6 Compound 6 3.79 42.53 516 Experimental Example 1-7 Compound 7 3.77 44.52 516 Experimental Example 1-8 Compound 8 3.68 42.54 517 Comparative Example 1-1 Comparative compound 1 5.78 38.47 517 Comparative Example 1-2 Comparative compound 2 5.90 37.21 517 Comparative Example 1-3 Comparative compound 3 5.67 36.11 517

As a result of the experiment, the green organic light-emitting devices of Experimental Examples 1-1 to 1-8 using the compounds represented by compounds 1 to 8 according to the present invention as a host material of the emission layer were Comparative Example 1- using Comparative Compounds 1 to 3 It exhibited superior performance in terms of current efficiency and driving voltage than green organic light-emitting devices of 1 to 1-3.

< Experimental example 2-1>

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

A hole injection layer (HIL; HAT-CN, 70 Å), a hole transport layer (HTL; NPB, 780 Å), an electron blocking layer (EBL; mCBP, 150 Å), a light emitting material layer (EML; compound 1 is used as a host) BDpyInCz doped 30% by weight with a delayed fluorescent material, 350 Å), a hole blocking layer (HBL; B3PYMPM; 100 Å), an electron transport layer (ETL: TPBi, 250 Å), an electron injection layer (EIL; LiF, 8 Å), Cathode (Al; 1000 Å).

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

<Experimental Example 2-2>

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

<Experimental Example 2-3>

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

<Experimental Example 2-4>

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

<Experimental Example 2-5>

An organic light-emitting device was manufactured in the same manner as in Experimental Example 2-1, except that Compound 5 was used instead of Compound 1 in Experimental Example 2-1.

<Experimental Example 2-6>

An organic light-emitting device was manufactured in the same manner as in Experimental Example 2-1, except that Compound 6 was used instead of Compound 1 in Experimental Example 2-1.

<Experimental Example 2-7>

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

<Experimental Example 2-8>

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

<Comparative Example 2-1>

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

<Comparative Example 2-2>

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

<Comparative Example 2-3>

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

When an electric current was applied to the organic light emitting devices fabricated in Experimental Examples 2-1 to 2-8 and Comparative Examples 2-1 to 2-3, the results of Table 2 were obtained.

compound
(Host) Voltage
(V@500cd/m ² ) EQE
(%) CIE x CIE y Experimental Example 2-1 Compound 1 4.35 8.7 0.173 0.266 Experimental Example 2-2 Compound 2 4.68 8.3 0.167 0.240 Experimental Example 2-3 Compound 3 4.29 8.8 0.162 0.204 Experimental Example 2-4 Compound 4 4.63 9.0 0.164 0.255 Experimental Example 2-5 Compound 5 4.40 8.1 0.175 0.259 Experimental Example 2-6 Compound 6 4.37 8.4 0.168 0.261 Experimental Example 2-7 Compound 7 4.40 8.6 0.173 0.270 Experimental Example 2-8 Compound 8 4.58 8.3 0.161 0.258 Comparative Example 2-1 Comparative compound 1 6.53 6.8 0.211 0.359 Comparative Example 2-2 Comparative compound 2 6.13 6.5 0.198 0.348 Comparative Example 2-3 Comparative compound 3 7.03 5.9 0.201 0.337

When the organic compound synthesized according to the present invention is used as a host of the delayed fluorescent light emitting material layer,

Compared with the case where Comparative Compounds 1 to 3 of Comparative Examples 2-1 to 2-3 were used as a host, the driving voltage was lowered and the external quantum efficiency (EQE) was improved. As a result, it was confirmed that the organic compound of the present invention was applied to the organic light emitting layer to lower the driving voltage of the light emitting diode, improve the luminous efficiency, and improve color purity. Accordingly, the organic light-emitting diode to which the organic compound of the present invention is applied can be used in light-emitting devices such as an organic light-emitting diode display device and/or a lighting device with lower power consumption and improved luminous efficiency and device life.

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

Claims (9)

Spiro compound represented by the following formula 1:
[Formula 1]

In Formula 1,
R1 is an unsubstituted carbazole group, a carbazole group substituted with a phenyl group, or a substituent represented by any one of the following formulas 3 to 6,
[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

In Formulas 1 and 3 to 6,
R2 to R6 are the same as or different from each other, and each independently hydrogen, deuterium, nitrile group, halogen group, substituted or unsubstituted alkyl group, substituted or unsubstituted silyl group, substituted or unsubstituted amine group, substituted or unsubstituted A substituted aryl group, or a substituted or unsubstituted heteroaryl group, or adjacent substituents may be bonded to each other to form a substituted or unsubstituted ring,
L is a direct bond; A substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,
When L is a direct bond, c is 1,
When R1 is an unsubstituted carbazole group or a carbazole group substituted with a phenyl group, L is a direct bond, a phenylene group or a divalent dibenzofuran group,
a, b and f are each an integer of 0 to 7,
c is an integer from 0 to 3,
When c is 0, L is a substituted or unsubstituted heteroarylene group,
d is an integer from 0 to 7,
e is an integer from 0 to 3,
When a is plural, R2 is the same as or different from each other,
When b is plural, R3 is the same as or different from each other,
When d is plural, R4 is the same as or different from each other,
When e is plural, R5 is the same as or different from each other,
When f is plural, R6 is the same as or different from each other,
R7 to R9 are the same as or different from each other, and each independently hydrogen, deuterium, nitrile group, halogen group, substituted or unsubstituted alkyl group, substituted or unsubstituted silyl group, substituted or unsubstituted amine group, substituted or unsubstituted A substituted aryl group, or a substituted or unsubstituted heteroaryl group,
Ar1 and Ar2 are the same as or different from each other, and each independently hydrogen, deuterium, nitrile group, halogen group, substituted or unsubstituted alkyl group, substituted or unsubstituted silyl group, substituted or unsubstituted amine group, substituted or unsubstituted A substituted aryl group, or a substituted or unsubstituted heteroaryl group,
g is an integer from 0 to 8,
h is an integer from 0 to 7,
i is an integer from 0 to 10,
When g is plural, R7 is the same as or different from each other,
When h is plural, R8 is the same as or different from each other,
When i is plural, R9 is the same as or different from each other.
delete The method of claim 1, wherein the formula 1 is a spiro compound represented by any one of the following formulas 7 to 9:
[Formula 7]

[Formula 8]

[Formula 9]

In Formula 7, R2, R3, a and b are as defined in Formulas 1 and 3 to 6,
c is an integer from 0 to 3,
R4 is hydrogen or a phenyl group, or a substituted or unsubstituted carbazole group,
L is a direct bond, a phenylene group or a divalent dibenzofuran group,
When L is a direct bond, c is 1,
In Formulas 8 and 9, R2, R3, R5, R6, a to c, e, and f are as defined in Formulas 1 and 3 to 6,
L is a direct bond; A substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,
R9 is hydrogen, deuterium, nitrile group, halogen group, substituted or unsubstituted alkyl group, substituted or unsubstituted silyl group, substituted or unsubstituted amine group, substituted or unsubstituted aryl group, or substituted or unsubstituted hetero Is an aryl group,
Ar3 is hydrogen, deuterium, a nitrile group, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted amine group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted hetero Is an aryl group,
i is an integer from 0 to 10, and when i is plural, R9 is the same as or different from each other. Spiro compound which is any one selected from the following compounds:

A first electrode; A second electrode provided opposite to the first electrode; And one or two or more organic material layers provided between the first electrode and the second electrode, wherein at least one of the organic material layers comprises the spiro compound of any one of claims 1, 3 and 4 The organic light emitting device. The organic light-emitting device of claim 5, wherein the organic material layer includes an emission layer, and the emission layer includes the spiro compound. The organic light-emitting device of claim 5, wherein the organic material layer includes an emission layer, and the emission layer includes the spiro compound as a host of the emission layer. The method according to claim 5, wherein the organic material layer comprises an emission layer, and a gap (ΔE _st ) between the lowest triplet state T1 and the first excitation singlet state S1 is ≦0.2 eV, including at least one compound as a dopant of the emission layer. The organic light emitting device. The organic light-emitting device of claim 5, wherein the organic material layer includes an emission layer, and the emission layer uses the spiro compound as a phosphorescent host of the emission layer.

Images