KR102250384B1 - Multicyclic compound and organic light emitting device comprising the same - Google Patents

Abstract

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

Description

A polycyclic compound and an organic light-emitting device including the same TECHNICAL FIELD [0002]

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

In the present specification, an organic light-emitting device is a light-emitting device using an organic semiconductor material, and requires an exchange of holes and/or electrons between an electrode and an organic semiconductor material. Organic light emitting devices can be divided into two types as follows according to the principle of operation. First, excitons are formed in the organic material layer by photons introduced into the device from an external light source, and these excitons are separated into electrons and holes, and these electrons and holes are transferred to different electrodes, and used as a current source (voltage source). It is a type of light emitting device. The second is a light emitting device in which holes and/or electrons are injected into an organic semiconductor material layer forming an interface with the electrode by applying voltage or current to two or more electrodes, and operated by the injected electrons and holes.

In general, the organic light emission phenomenon refers to a phenomenon in which electrical energy is converted into light energy by using an organic material. 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 multilayer 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. When it falls back to the ground, it glows. These organic light emitting devices are known to have characteristics such as self-luminescence, high luminance, high efficiency, low driving voltage, wide viewing angle, and high contrast.

Materials used as the organic material layer in the organic light-emitting device can be classified into light-emitting materials and charge transport materials, such as hole injection materials, hole transport materials, electron transport materials, and electron injection materials, according to their functions. Light-emitting materials include blue, green, and red light-emitting materials and yellow and orange light-emitting materials necessary to realize better natural colors according to the light-emitting color.

In addition, in order to increase color purity and increase luminous efficiency through energy transfer, a host/dopant system may be used as a luminescent material. The principle is that when a small amount of a dopant having an energy band gap smaller than that of a host constituting the light emitting layer and having excellent light emission efficiency is mixed in a light emitting layer, excitons generated from the host are transported as a dopant to emit light with high efficiency. At this time, since the wavelength of the host moves to the wavelength of the dopant, light having a desired wavelength can be obtained according to the type of dopant used.

In order to fully exhibit the excellent characteristics of the above-described organic light emitting device, materials that form the organic material layer in the device, such as hole injection materials, hole transport materials, light-emitting materials, electron transport materials, electron injection materials, etc., are supported by stable and efficient materials. The development of new materials continues to be required.

Korean Patent Publication No. 2011-108575

In the present specification, a polycyclic compound and an organic light-emitting device including the same are described.

An exemplary embodiment of the present specification provides a compound represented by Formula 1 below.

[Formula 1]

In Formula 1,

R is hydrogen; heavy hydrogen; A substituted or unsubstituted amine group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,

R1 and R2 are each independently hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group; Or a substituted or unsubstituted aryl group.

In addition, according to an exemplary 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 of the organic material layers includes the compound.

The compounds described herein can be used as a material for an organic material layer of an organic light-emitting device. The compound according to at least one exemplary embodiment may improve lifespan characteristics and/or in an organic light-emitting device. In particular, the compounds described herein can be used as a material for a hole injection layer, a hole transport layer, an electron suppression layer, a light-emitting layer, a hole suppression layer, an electron transport layer, and an electron injection layer.

1 shows an example of an organic light-emitting device comprising a substrate 1, an anode 2, 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, an electron suppression layer 6, a light-emitting layer 7, an electron transport layer 8, and a cathode 4 It is shown.

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

The present specification provides a compound represented by the following formula (1). When the compound represented by the following formula (1) is used in the organic material layer of the organic light-emitting device, the efficiency of the organic light-emitting device is always maintained.

[Formula 1]

In Formula 1,

R is hydrogen; heavy hydrogen; A substituted or unsubstituted amine group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,

R1 and R2 are each independently hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group; Or a substituted or unsubstituted aryl group.

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.

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

Examples of the substituent 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; Halogen group; Cyano group; Alkyl group; Cycloalkyl group; Arylamine group; Aryl group; And it is substituted with one or two or more substituents selected from the group consisting of a heterocyclic group, two or more of the substituents exemplified above are substituted with a connected substituent, or does not have any substituents. For example, "a substituent to which two or more substituents are connected" 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.

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

In the present specification, examples of the halogen group include fluorine (F), chlorine (Cl), bromine (Br), or iodine (I).

In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 60. According to an exemplary embodiment, the alkyl group has 1 to 30 carbon atoms. According to another 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. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-oxy And the like, but are not limited to these.

In the present specification, the cycloalkyl group is not particularly limited, but is preferably 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, there are a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and the like, but are not limited thereto.

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

Specific examples of the arylamine group include phenylamine group, naphthylamine group, biphenylamine group, anthracenylamine group, 3-methyl-phenylamine group, 4-methyl-naphthylamine group, 2-methyl-biphenylamine Group, 9-methyl-anthracenylamine group, diphenyl amine group, phenyl naphthyl amine group, biphenyl phenyl amine group, and the like, but are not limited thereto.

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 an exemplary embodiment, the aryl group has 6 to 30 carbon atoms. According to an exemplary embodiment, the aryl group has 6 to 20 carbon atoms. The aryl group may be a phenyl group, a biphenyl group, or a terphenyl group, but the monocyclic aryl group is not limited thereto. The polycyclic aryl group may be a naphthyl group, an anthracenyl group, a phenanthrenyl group, a pyrenyl group, a perylenyl group, a triphenyl group, a chrysenyl group, a fluorenyl group, and the like, but is not limited thereto.

In the present specification, the fluorenyl group may be substituted, and two substituents may be bonded to each other to form a spiro structure.

,

등의 스피로플루오레닐기,

(9,9-디메틸플루오레닐기), 및

(9,9-디페닐플루오레닐기) 등의 치환된 플루오레닐기가 될 수 있다. 다만, 이에 한정되는 것은 아니다.When the fluorenyl group is substituted,

,

Spirofluorenyl groups such as,

(9,9-dimethylfluorenyl group), and

It may be a substituted fluorenyl group such as (9,9-diphenylfluorenyl group). However, it is not limited thereto.

In the present specification, the heterocyclic group is a cyclic group including at least one of N, O, P, S, Si, and Se as hetero atoms, and the number of carbons is not particularly limited, but is preferably 2 to 60 carbon atoms. According to an exemplary embodiment, the number of carbon atoms of the heterocyclic group is 2 to 30. Examples of the heterocyclic group include a pyridyl group, a pyrrole group, a pyrimidyl group, a pyridazinyl group, a furanyl group, a thiophenyl group, an imidazole group, a pyrazole group, a dibenzofuranyl group, a dibenzothiophenyl group, and the like. It is not limited to only.

In the present specification, the description of the aforementioned heterocyclic group may be applied except that the heteroaryl group is aromatic.

In this specification, "adjacent" The group may mean a substituent substituted on an atom directly connected to the atom where the corresponding substituent is substituted, a substituent positioned three-dimensionally closest to the corresponding substituent, or another substituent substituted on an atom in which the corresponding substituent is substituted. For example, two substituents substituted with an ortho position in a benzene ring and two substituents substituted with the same carbon in an aliphatic ring may be interpreted as "adjacent" to each other.

In the present specification, in a substituted or unsubstituted ring formed by bonding of adjacent groups to each other, "ring" is a hydrocarbon ring; Or it means a heterocycle.

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

In the present specification, description of an aryl group may be applied except that the aromatic hydrocarbon ring is monovalent.

In the present specification, the heterocycle is an atom other than carbon and contains one or more heteroatoms, and specifically, the heteroatoms include one or more atoms selected from the group consisting of N, O, P, S, Si, and Se, etc. can do. The heterocycle may be monocyclic or polycyclic, and may be an aromatic, aliphatic, or condensed ring of aromatic and aliphatic, and the aromatic heterocycle may be selected from examples of the heteroaryl group except that it is not monovalent.

According to an exemplary embodiment of the present specification, R is each independently hydrogen; heavy hydrogen; A substituted or unsubstituted amine group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted arylamine group having 6 to 60 carbon atoms; A substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Or a substituted or unsubstituted C2 to C60 heterocyclic group.

According to an exemplary embodiment of the present specification, R is each independently hydrogen; heavy hydrogen; A substituted or unsubstituted amine group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted arylamine group having 6 to 30 carbon atoms; A substituted or unsubstituted aryl group having 6 to 30 carbon atoms; Or a substituted or unsubstituted C2 to C30 heterocyclic group.

According to an exemplary embodiment of the present specification, R is each independently hydrogen; heavy hydrogen; A substituted or unsubstituted amine group; A substituted or unsubstituted arylamine group having 6 to 30 carbon atoms; A substituted or unsubstituted aryl group having 6 to 30 carbon atoms; Or a substituted or unsubstituted C2 to C30 heterocyclic group.

According to an exemplary embodiment of the present specification, R1 and R2 are each independently hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group; Or a substituted or unsubstituted aryl group.

According to an exemplary embodiment of the present specification, R1 and R2 are each independently hydrogen; heavy hydrogen; A substituted or unsubstituted C1-C60 alkyl group; Or a substituted or unsubstituted aryl group having 6 to 60 carbon atoms.

According to an exemplary embodiment of the present specification, R1 and R2 are each independently hydrogen; heavy hydrogen; A substituted or unsubstituted C1-C30 alkyl group; Or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms.

According to an exemplary embodiment of the present specification, R1 and R2 are each independently hydrogen; heavy hydrogen; A substituted or unsubstituted C1-C15 alkyl group; Or a substituted or unsubstituted aryl group having 6 to 15 carbon atoms.

According to an exemplary embodiment of the present specification, R1 and R2 are each independently hydrogen; heavy hydrogen; Or a substituted or unsubstituted C 1 to C 15 alkyl group.

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

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

[Formula 2]

[Formula 3]

In Formulas 2 and 3,

The definitions of R, R1 and R2 are as described above.

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

[Formula 4]

[Formula 5]

In Formulas 4 and 5,

The definitions of R, R1 and R2 are the same as in Chemical Formula 1.

In the exemplary embodiment of the present specification, Formula 1 may be represented by any one of the following structures.

The compound of Formula 1 according to an exemplary embodiment of the present specification may be prepared by a method described below.

For example, the compound of Formula 1 may have a core structure as shown in Schemes A to D below. Substituents may be bonded by methods known in the art, and the type, position, or number of substituents may be changed according to techniques known in the art.

<Reaction Scheme A>

<Reaction Scheme B>

<Reaction Scheme C>

<Reaction Scheme D>

The intermediates prepared according to Schemes A to D are as follows.

The conjugation length and energy bandgap of a compound are closely related. Specifically, the longer the conjugation length of the compound, the smaller the energy band gap.

In the present invention, compounds having various energy band gaps can be synthesized by introducing various substituents into the core structure as described above. In addition, in the present invention, the HOMO and LUMO energy levels of the compound can be adjusted by introducing various substituents to the core structure of the above structure.

In addition, by introducing various substituents into the core structure of the above structure, a compound having the inherent characteristics of the introduced substituent can be synthesized. For example, by introducing a substituent mainly used for the hole injection layer material, the hole transport material, the emission layer material, and the electron transport layer material used in the manufacture of an organic light emitting device into the core structure, it is possible to synthesize a material that satisfies the conditions required by each organic material layer. I can.

In addition, the organic light emitting device according to the present invention includes 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 of the organic material layers includes the compound of Formula 1.

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 using the above-described compound.

The compound 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 coating method refers to spin coating, dip coating, inkjet printing, screen printing, spray method, roll coating, and the like, but is not limited thereto.

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 the organic light-emitting device of the present invention, the organic material layer may include an electron transport layer or an electron injection layer, and the electron transport layer or the electron injection layer may include the compound represented by Formula 1 above.

In the organic light-emitting device of the present invention, the organic material layer may include a hole injection layer or a hole transport layer, and the hole injection layer or the hole transport layer may include the compound represented by Formula 1 above.

In another exemplary embodiment, the organic material layer includes an emission layer, and the emission layer includes a compound represented by Formula 1 above.

According to another exemplary embodiment, the organic material layer may include an emission layer, and the emission layer may include the compound represented by Formula 1 as a dopant of the emission layer.

In another exemplary embodiment, the organic material layer including the compound represented by Formula 1 includes the compound represented by Formula 1 as a dopant, includes a fluorescent host or a phosphorescent host, and other organic compounds, metals, or metal compounds May be included as a dopant.

As another example, the organic material layer including the compound represented by Formula 1 includes the compound represented by Formula 1 as a dopant, includes a fluorescent host or a phosphorescent host, and can be used together with an iridium-based (Ir) dopant. have.

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

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

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

1 illustrates a structure of an organic light-emitting device in which an anode 2, a light emitting layer 3, and a cathode 4 are sequentially stacked on a substrate 1. In such a structure, the compound may be included in the emission layer 3.

2, an organic light emitting device in which an anode 2, a hole injection layer 5, an electron suppression layer 6, a light emitting layer 7, an electron transport layer 8, and a cathode 4 are sequentially stacked on a substrate 1 The structure of is illustrated. In such a structure, the compound may be included in the hole injection layer 5, the electron suppression layer 6, the emission layer 7 or the electron transport layer 8.

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. It can be prepared by depositing an anode to form an anode, forming an organic material layer including a hole injection layer, an electron suppressing layer, a light emitting layer, and an electron transport layer thereon, and then depositing a material that can be used as a cathode thereon. In addition to this method, an organic light-emitting device may be manufactured by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate.

The organic material layer may have a multilayer structure including a hole injection layer, an electron suppression layer, an emission layer, an electron transport layer, and the like, but is not limited thereto and may have a single layer structure. In addition, the organic material layer is made of a variety of polymer materials, and is used in a smaller number of solvent processes, such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer. It can be made in layers.

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 anode 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); ZnO: Al or SnO _2: a combination of a metal and an oxide such as Sb; Poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), conductive polymers such as polypyrrole and polyaniline, and the like, 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 multilayered 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. Organic substances, anthraquinone, polyaniline, and polythiophene-based conductive polymers, but are not limited thereto.

As the hole transport material, a material capable of transporting holes from an anode or a hole injection layer to the light emitting layer and 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 emission layer may emit red, green, or blue light, and may be made of a phosphorescent material or a fluorescent material. As the light-emitting material, a material capable of emitting light in a visible light region by transporting and combining holes and electrons from the electron suppressing layer and the electron transport layer, respectively, and a material having good quantum efficiency against fluorescence or phosphorescence is preferable. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq ₃ ); Carbazole-based compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzoquinoline-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.

Examples of the host material for the light emitting layer include a condensed aromatic ring derivative or a heterocyclic compound. Specifically, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, and fluoranthene compounds, and heterocycle-containing compounds include carbazole derivatives, dibenzofuran derivatives, ladder type Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.

The iridium-based complex used as a dopant of the light emitting layer is as follows, but is not limited thereto.

[Ir(piq) ₃ ] [Btp ₂ Ir(acac)]

[Ir(ppy) ₃ ] [Ir(ppy) ₂ (acac)]

[Ir(mpyp) ₃ ] [F ₂ Irpic]

[(F ₂ ppy) ₂ Ir(tmd)] [Ir(dfppz) ₃ ]

　　　

　　　

The electron transport material is a material capable of receiving electrons from the cathode and transferring them to the light emitting layer, and a material having high mobility for electrons is suitable. Specific examples include Al complex of 8-hydroxyquinoline; Complexes containing Alq _3; Organic radical compounds; Hydroxyflavone-metal complexes and the like, but are not limited thereto.

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

Fabrication of an organic light-emitting device including the compound represented by Formula 1 will be described in detail in the following Examples. However, the following examples are for illustrative purposes only, and the scope of the present specification is not limited thereto.

Manufacturing Example 1

Compound A (7.50 g, 17.01 mmol) and compound a1 (8.64 g, 19.56 mmol) were completely dissolved in 240 mL of tetrahydrofuran in a 500 mL round-bottom flask in a nitrogen atmosphere, and then 2M aqueous potassium carbonate solution (120 mL) was added. , Tetrakis-(triphenylphosphine)palladium (0.59 g, 0.51 mmol) was added, followed by heating and stirring for 3 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 210 mL of ethyl acetate to prepare Preparation Example 1 (10.06 g, 78%).

MS[M+H] ⁺ = 691

Manufacturing Example 2

Compound B (7.50 g, 17.01 mmol) and compound a2 (9.41 g, 19.56 mmol) were completely dissolved in 220 mL of tetrahydrofuran in a 500 mL round-bottom flask in a nitrogen atmosphere, and then 2M aqueous potassium carbonate solution (110 mL) was added. , Tetrakis-(triphenylphosphine)palladium (0.59 g, 0.51 mmol) was added, followed by heating and stirring for 2 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 160 mL of ethyl acetate to prepare Preparation Example 2 (8.67 g, 64%).

MS[M+H] ⁺ = 781

Manufacturing Example 3

Compound C (7.50 g, 17.01 mmol) and compound a3 (9.41 g, 19.56 mmol) were completely dissolved in 220 mL of tetrahydrofuran in a 500 mL round bottom flask in a nitrogen atmosphere, and then 2M aqueous potassium carbonate solution (110 mL) was added. , Tetrakis-(triphenylphosphine)palladium (0.59 g, 0.51 mmol) was added, followed by heating and stirring for 2 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 160 mL of ethyl acetate to prepare Preparation Example 3 (8.67 g, 64%).

MS[M+H] ⁺ = 797

Manufacturing Example 4

Compound A-1 (7.29 g, 16.72 mmol) and compound a4 (5.64 g, 17.56 mmol) were completely dissolved in 220 mL of Xylene in a 500 mL round-bottom flask in a nitrogen atmosphere, and NaOtBu (2.09 g, 21.74 mmol) was added thereto. , Bis (tri- tert- butylphosphine) palladium (0) (0.09 g, 0.17 mmol) was added, followed by heating and stirring for 3 hours. After lowering the temperature to room temperature and removing the base by filtering, Xylene was concentrated under reduced pressure and recrystallized with 160 mL of ethyl acetate to prepare Preparation Example 4 (7.75 g, yield: 68%).

MS[M+H] ⁺ = 803

Manufacturing Example 5

Compound C (7.29 g, 16.72 mmol) and compound a5 (5.64 g, 17.56 mmol) were completely dissolved in 220 mL of Xylene in a nitrogen atmosphere, and NaOtBu (2.09 g, 21.74 mmol) was added, followed by Bis. (tri- tert- butylphosphine) palladium(0) (0.09 g, 0.17 mmol) was added, followed by heating and stirring for 3 hours. After lowering the temperature to room temperature and removing the base by filtering, Xylene was concentrated under reduced pressure and recrystallized with 160 mL of ethyl acetate to prepare Preparation Example 5 (7.75 g, yield: 68%).

MS[M+H] ⁺ = 755

Manufacturing Example 6

Compound B-1 (7.29 g, 16.72 mmol) and compound a6 (5.64 g, 17.56 mmol) were completely dissolved in 220 mL of Xylene in a 500 mL round bottom flask in a nitrogen atmosphere, and NaOtBu (2.09 g, 21.74 mmol) was added. , Bis (tri- tert- butylphosphine) palladium (0) (0.09 g, 0.17 mmol) was added, followed by heating and stirring for 3 hours. After lowering the temperature to room temperature and removing the base by filtering, Xylene was concentrated under reduced pressure and recrystallized with 160 mL of ethyl acetate to prepare Preparation Example 6 (7.75 g, yield: 68%).

MS[M+H] ⁺ = 803

Manufacturing Example 7

Compound D (7.29 g, 16.72 mmol) and compound a7 (5.64 g, 17.56 mmol) were completely dissolved in 220 mL of Xylene in a 500 mL round-bottom flask in a nitrogen atmosphere, and NaOtBu (2.09 g, 21.74 mmol) was added, and Bis (tri- tert- butylphosphine) palladium(0) (0.09 g, 0.17 mmol) was added, followed by heating and stirring for 3 hours. After lowering the temperature to room temperature and removing the base by filtering, Xylene was concentrated under reduced pressure and recrystallized with 160 mL of ethyl acetate to prepare Preparation Example 7 (7.75 g, yield: 68%).

MS[M+H] ⁺ = 652

Example 1-1

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

A hole injection layer was formed by thermally vacuum evaporating a compound of the following compound HI1 and the following compound HI2 to a thickness of 100 Å in a ratio of 98:2 (molar ratio) on an ITO transparent electrode, which is an anode thus prepared. A hole transport layer was formed by vacuum depositing a compound (1150Å) represented by the following formula HT1 on the hole injection layer. Subsequently, the compound of Preparation Example 1 was vacuum-deposited on the hole transport layer with a film thickness of 50 Å to form an electron suppressing layer. Subsequently, a light emitting layer was formed by vacuum depositing a compound represented by the following formula BH and a compound represented by the following formula BD with a film thickness of 200 Å on the electron suppressing layer at a weight ratio of 25:1. A hole blocking layer was formed by vacuum depositing a compound represented by the following Chemical Formula HB1 with a film thickness of 50 Å on the emission layer. Subsequently, a compound represented by the following formula ET1 and a compound represented by the following formula LiQ were vacuum-deposited at a weight ratio of 1:1 on the hole blocking layer to form an electron injection and transport layer with a thickness of 310Å. Lithium fluoride (LiF) in a thickness of 12 Å and aluminum in a thickness of 1,000 Å were sequentially deposited on the electron injection and transport layer to form a negative electrode.

In the above process, the deposition rate of the organic material was maintained at 0.4 ~ 0.7Å/sec, the deposition rate of lithium fluoride at the cathode was 0.3Å/sec, and the deposition rate of aluminum was 2Å/sec, and the vacuum degree during deposition was 2x10 ^-7 ~ An organic light emitting device was manufactured by maintaining ^{5x10 -6 torr.}

Example 1-2 and Example 1-3

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

Comparative example 1-1 to 1-3

An organic light-emitting device was manufactured in the same manner as in Example 1-1, except that the compound shown in Table 1 was used instead of the compound of Preparation Example 1. The compounds of EB2, EB3, and EB 4 used in Table 1 are as follows.

Experimental Example 1

When a current was applied to the organic light emitting device prepared in the above Examples and Comparative Examples, voltage, efficiency, color coordinates, and lifetime were measured, and the results are shown in Table 1 below. T95 refers to the time it takes for the luminance to decrease from the initial luminance (1600 nit) to 95%.

compound
(Electronic suppression layer) Voltage
(V@10mA
/cm ² ) efficiency
(cd/A@10mA
/cm ² ) Color coordinates
(x,y) T95
(hr) Example 1-1 Manufacturing Example 1 4.51 6.22 (0.138, 0.044) 290 Example 1-2 Manufacturing Example 2 4.53 6.21 (0.140, 0.043) 285 Example 1-3 Manufacturing Example 3 4.46 6.43 (0.139, 0.043) 270 Comparative Example 1-1 EB2 5.12 5.75 (0.139, 0.043) 125 Comparative Example 1-2 EB3 5.67 5.02 (0.142, 0.045) 165 Comparative Example 1-3 EB4 7.25 4.16 (0.150, 0.049) 50

As shown in Table 1, the organic light-emitting device using the compound of the present invention as an electron suppressing layer exhibited excellent characteristics in terms of efficiency, driving voltage, and stability of the organic light-emitting device.

The organic light-emitting device including the compound according to an exemplary embodiment of the present specification describes Comparative Examples EB2 and EB3 in which the core structure includes O or S, and the same core structure as the core structure of the present application, but a substituent group on the condensed ring Compared to the organic light emitting device manufactured using the contained EB4 material, it exhibited the characteristics of low voltage, high efficiency, and long life.

Comparative Example 1-2 using the EB2 material containing an amine group has better properties than Comparative Example 1-3 using the EB3 material containing a fluorene group, but overall inferior to Examples 1-1 to 1-3 of the present invention Got it.

In particular, Comparative Example 1-3 obtained a result that the structure of the material became bulky on both sides, resulting in a large increase in voltage, a decrease in efficiency, and a remarkably low lifespan.

As shown in the results of Table 1, it was confirmed that the compound according to the present invention has excellent electron blocking ability and thus can be applied to an organic light-emitting device.

Example 2-1 to Example 2-4

An organic light-emitting device was manufactured in the same manner as in Example 1-1, except that the compound EB1 was used instead of the compound of Preparation Example 1 and the compound shown in Table 2 below was used instead of ET1.

Comparative example 2-1 and 2-2

An organic light-emitting device was manufactured in the same manner as in Example 1-1, except that the compound EB1 was used instead of the compound of Preparation Example 1 and the compound shown in Table 2 below was used instead of ET1.

The compounds of ET2 and ET3 used in Table 1 are as follows.

When a current was applied to the organic light-emitting devices manufactured according to Experimental Examples 2-1 to 2-4, Comparative Example 2-1 and Comparative Example 2-2, voltage, efficiency, color coordinates, and lifetime were measured, and the results are shown below It is shown in Table 2]. T95 refers to the time it takes for the luminance to decrease from the initial luminance (1600 nits) to 95%.

compound
(Electron transport layer) Voltage
(V@10Ma
/cm ² ) efficiency
(cd/A@10mA
/cm ² ) Color coordinates
(x,y)
T95
(hr) Experimental Example 2-1 Compound 1 4.41 45.82 (0.141, 0.046) 270 Experimental Example 2-2 Compound 2 4.56 46.63 (0.138, 0.044) 275 Experimental Example 2-3 Compound 3 4.54 46.45 (0.142, 0.044) 285 Experimental Example 2-4 Compound 4 4.58 45.81 (0.140, 0.046) 270 Comparative Example 2-1 ET 2 5.15 43.71 (0.143, 0.047) 235 Comparative Example 2-2 ET 3 5.22 43.33 (0.143, 0.049) 215

As shown in Table 1, in the case of an organic light-emitting device manufactured using the compound of the present invention as an electron transport layer, the organic light-emitting device exhibits excellent characteristics in terms of efficiency, driving voltage and/or stability.

Compared to the organic light emitting device manufactured using the materials of Comparative Examples ET2 and ET3 in which the core structure contains O or S, the characteristics of low voltage, high efficiency, and long life were shown.

In particular, the devices of Comparative Examples 2-1 to 2-2 increased significantly in terms of voltage than the compound of the present invention. This is because the core of the present invention is a fluorene type and contains more electrons than the structure containing O or S. This is because more electrons can be transferred to the light-emitting layer through the suppression layer, and the voltage drops.

Although the preferred embodiments of the present invention (electron suppression layer, electron transport layer) have been described above, the present invention is not limited thereto, and various modifications can be made within the scope of the claims and detailed description of the invention And this also belongs to the scope of the invention.

1: substrate
2: anode
3: light-emitting layer
4: cathode
5: hole injection layer
6: hole transport layer
7: light emitting layer
8: electron transport layer

Claims (8)

A compound represented by the following Formula 1:
[Formula 1]

In Formula 1,
R is hydrogen; heavy hydrogen; A substituted or unsubstituted amine group; A substituted or unsubstituted C1 to C20 alkylamine group; A substituted or unsubstituted arylamine group having 6 to 60 carbon atoms; A substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Or a substituted or unsubstituted C2 to C60 heterocyclic group,
R1 and R2 are each independently hydrogen; heavy hydrogen; A substituted or unsubstituted C1-C15 alkyl group; Or a substituted or unsubstituted aryl group having 6 to 15 carbon atoms. The method according to claim 1,
Formula 1 is a compound represented by the following Formula 2 or 3:
[Formula 2]

[Formula 3]

In Formulas 2 and 3,
The definitions of R, R1 and R2 are the same as in Chemical Formula 1. The method according to claim 1,
Formula 1 is a compound represented by the following formula 4 or 5:
[Formula 4]

[Formula 5]

In Formulas 4 and 5,
The definitions of R, R1 and R2 are the same as in Chemical Formula 1. The method according to claim 1,
Formula 1 is a compound that is any one selected from the following structural formulas:

. 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 of the organic material layers contains the compound according to any one of claims 1 to 4 Light-emitting element. The method of claim 5,
The organic material layer includes a hole injection layer or an electron suppression layer, and the hole injection layer or the electron suppression layer includes the compound of Formula 1. The method of claim 5,
The organic material layer includes an electron transport layer or an electron injection layer, and the electron transport layer or the electron injection layer includes the compound of Formula 1. The method of claim 5,
The organic material layer includes an emission layer, and the emission layer includes the compound of Formula 1 above.

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