KR102665294B1 - Novel compound and organic light emitting device comprising the same - Google Patents

Abstract

The present invention provides a novel compound and an organic light-emitting device using the same.

Description

Novel compound and organic light emitting device comprising the same}

The present invention relates to novel compounds and organic light-emitting devices containing them.

In general, organic luminescence refers to a phenomenon that converts electrical energy into light energy using organic materials. Organic light-emitting devices using the organic light-emitting phenomenon have a wide viewing angle, excellent contrast, fast response time, and excellent luminance, driving voltage, and response speed characteristics, so much research is being conducted.

Organic light emitting devices generally have a structure including an anode, a cathode, and an organic material layer between the anode and the cathode. The organic material layer is often composed of a multi-layer structure made of different materials to increase the efficiency and stability of the organic light-emitting device, and may be composed of, for example, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, and an electron injection layer. In the structure of this organic light-emitting device, when a voltage is applied between the two electrodes, holes are injected from the anode and electrons from the cathode into the organic material layer. When the injected holes and electrons meet, an exciton is formed, and this exciton When it falls back to the ground state, it glows.

The development of new materials for organic materials used in organic light-emitting devices as described above is continuously required.

Korean Patent Publication No. 10-2000-0051826

The present invention relates to novel compounds and organic light-emitting devices containing them.

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

[Formula 1]

In Formula 1,

L ₁ to L ₃ are each independently a single bond; Substituted or unsubstituted C _6-60 arylene; or a C _2-60 heteroarylene containing one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S,

A is phenanthrenyl, triphenylenyl, dibenzofuranyl, or dibenzothiophenyl,

Here, A is unsubstituted or consists of C _2-20 heteroaryl containing one or more heteroatoms selected from the group consisting of C _1-20 alkyl, C _6-20 aryl, and N, O, and S. is substituted with one or more substituents each independently selected from the group,

B is a substituent represented by the following formula 2,

Ar is a substituent represented by the following formula (2); Substituted or unsubstituted C _6-60 aryl; or C _2-60 heteroaryl containing one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S,

[Formula 2]

In Formula 2,

X is O or S,

One of R ₁ to R ₃ is bonded to L ₂ or L ₃ , and the others are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted C _1-60 alkyl; Substituted or unsubstituted C _6-60 aryl; or C _2-60 heteroaryl containing one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S,

However, when L ₂ or L ₃ is bonded to R ₁ or R ₂ , unbonded R ₁ or R ₂ is not hydrogen,

n is an integer from 1 to 4.

In addition, the present invention includes a first electrode; a second electrode provided opposite to the first electrode; And an organic light-emitting device comprising one or more organic material layers provided between the first electrode and the second electrode, wherein one or more layers of the organic material layers include a compound represented by Formula 1. .

The compound represented by the above-described formula 1 can be used as a material for the organic layer of an organic light-emitting device, and can improve efficiency, low driving voltage, and/or lifespan characteristics of the organic light-emitting device.

Figure 1 shows an example of an organic light emitting device consisting of a substrate 1, an anode 2, a hole transport layer 3, a light emitting layer 4, an electron injection and transport layer 5, and a cathode 6.
Figure 2 shows the substrate (1), anode (2), hole injection layer (7), hole transport layer (3), hole control layer (8), light emitting layer (4), electron control layer (9), electron injection and transport layer ( 5) and a cathode 6. An example of an organic light-emitting device is shown.

Hereinafter, the present invention will be described in more detail to aid understanding.

Definition of Terms

는 다른 치환기에 연결되는 결합을 의미한다.In this specification, and

means a bond connected to another substituent.

As used herein, the term “substituted or unsubstituted” refers to deuterium; halogen group; Cyano group; nitro group; hydroxyl group; carbonyl group; ester group; imide group; amino group; Phosphine oxide group; Alkoxy group; Aryloxy group; Alkylthioxy group; Arylthioxy group; Alkyl sulphoxy group; Aryl sulfoxy group; silyl group; boron group; Alkyl group; Cycloalkyl group; alkenyl group; Aryl group; Aralkyl group; Aralkenyl group; Alkylaryl group; Alkylamine group; Aralkylamine group; heteroarylamine group; Arylamine group; Arylphosphine group; or substituted or unsubstituted with one or more substituents selected from the group consisting of heteroaryl containing one or more of N, O and S atoms, or substituted or unsubstituted with two or more of the above-exemplified substituents linked. . For example, “a substituent group in which two or more substituents are connected” may be a biphenyl group. That is, the biphenyl group may be an aryl group, or it may be interpreted as a substituent in which two phenyl groups are connected.

In this specification, the carbon number of the carbonyl group is not particularly limited, but is preferably 1 to 40 carbon atoms. Specifically, it may be a compound with the following structure, but is not limited thereto.

In the present specification, the oxygen of the ester group may be substituted with a straight-chain, branched-chain, or ring-chain alkyl group having 1 to 25 carbon atoms or an aryl group having 6 to 25 carbon atoms. Specifically, it may be a compound of the following structural formula, but is not limited thereto.

In this specification, the carbon number of the imide group is not particularly limited, but is preferably 1 to 25 carbon atoms. Specifically, it may be a compound with the following structure, but is not limited thereto.

In the present specification, the silyl group specifically includes trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, phenylsilyl group, etc. However, it is not limited to this.

In this specification, the boron group specifically includes trimethyl boron group, triethyl boron group, t-butyldimethyl boron group, triphenyl boron group, and phenyl boron group, but is not limited thereto.

In this specification, examples of halogen groups include fluorine, chlorine, bromine, or iodine.

In the present specification, the alkyl group may be straight chain or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to one embodiment, the carbon number of the alkyl group is 1 to 20. According to another embodiment, the carbon number of the alkyl group is 1 to 10. According to another embodiment, the carbon number of the alkyl group is 1 to 6. Specific examples of alkyl groups 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 -Dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, etc., but is not limited to these.

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

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

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

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

It can be etc. However, it is not limited to this.

In the present specification, heteroaryl is a heteroaryl containing one or more of O, N, Si, and S as a heteroelement, and the number of carbon atoms is not particularly limited, but is preferably 2 to 60 carbon atoms. Examples of heteroaryl include thiophene group, furan group, pyrrole group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, pyrimidyl group, triazine group, acridyl group, Pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidinyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group, isoquinoline group, indole group, Carbazole group, benzooxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group, isoxazolyl group, thiadiazolyl group group, phenothiazinyl group, and dibenzofuranyl group, but are not limited to these.

In this specification, the aryl group among the aralkyl group, aralkenyl group, alkylaryl group, arylamine group, and arylsilyl group is the same as the example of the aryl group described above. In this specification, the aralkyl group, alkylaryl group, and alkylamine group are the same as the examples of the alkyl group described above. In the present specification, the description regarding heteroaryl described above may be applied to heteroaryl among heteroarylamines. In this specification, the alkenyl group among the aralkenyl groups is the same as the example of the alkenyl group described above. In this specification, the description of the aryl group described above can be applied, except that arylene is a divalent group. In the present specification, the description of heteroaryl described above can be applied, except that heteroarylene is a divalent group. In the present specification, the description of the aryl group or cycloalkyl group described above can be applied, except that the hydrocarbon ring is not monovalent and is formed by combining two substituents. In the present specification, the description of heteroaryl described above can be applied, except that the heterocycle is not monovalent and is formed by combining two substituents.

compound

Meanwhile, the present invention provides an amine-based compound represented by Formula 1 above.

The amine-based compound represented by Formula 1 contains a substituent of any one of phenanthrenyl, triphenylenyl, dibenzofuranyl, and dibenzothiophenyl and a substituent of any one of benzofuranyl and benzothiophenyl, Organic light emitting devices using this can achieve high efficiency, low driving voltage, and long lifespan. In addition, the benzofuranyl or benzothiophenyl substituent is represented by Formula 2, wherein any one of phenanthrenyl, triphenylenyl, dibenzofuranyl, and dibenzothiophenyl substituent and R ₁ of Formula 2 Or, when bonded to R ₂ , the organic light-emitting device employing a compound in which R ₁ or R ₂ is not bonded is hydrogen, compared to the organic light-emitting device employing the compound represented by Formula 1, as will be confirmed in the comparative example described later. As can be seen, it is excluded from the present invention due to its high voltage, low efficiency, and poor lifespan characteristics.

In Formula 1, preferably, L ₁ to L ₃ are each independently a single bond, phenylene, biphenyldiyl, or naphthylene.

More preferably, L ₁ to L ₃ are each independently a single bond or any one selected from the group consisting of:

.

.

Preferably, A is phenanthrenyl, triphenylenyl, dibenzofuranyl, or dibenzothiophenyl, wherein A is unsubstituted or consists of C _1-20 alkyl and C _6-60 aryl. is substituted with 1 to 3 substituents each independently selected from the group.

More preferably, A is represented by any one of the following formulas a1 to a4.

In the above formulas a1 to a4,

Each R is independently hydrogen, or C _6-20 aryl.

At this time, two R in formulas a3 and a4 may be the same or different from each other, for example, R is each independently hydrogen, phenyl, or naphthyl.

Preferably, in Formula 2, R ₁ to R ₃ that are not bonded to L ₂ or L ₃ are each independently hydrogen, deuterium, C _1-10 alkyl, or C _6-20 aryl, and n is 1, 2 , or 3. At this time, when n is 2 or more, R ₃ is the same or different from each other.

More preferably, the substituent represented by Formula 2 is represented by any one of the following formulas b1 to b3:

In the above formulas b1 to b3,

X is O or S,

R ₁ and R ₂ are each independently C _1-10 alkyl, or C _6-20 aryl,

R ₃ and R ₁ ' to R ₃ ' are each independently hydrogen, C _1-10 alkyl, C _6-20 aryl, or C _2-20 heteroaryl containing a heteroatom O or S, and 2 in formula b2 R ₃ may be the same or different from each other.

Most preferably, in formulas b1 and b2,

R ₁ is methyl, ethyl, phenyl, biphenylyl, or naphthyl,

R ₂ is methyl, ethyl, phenyl, or biphenylyl,

R ₃ is each independently hydrogen, methyl, or phenyl,

In formula b3,

R ₁ ' to R ₃ ' are each independently hydrogen, methyl, isopropyl, naphthyl, phenyl, or dibenzothiophenyl.

Preferably, Ar is a substituent represented by Formula 2 above; Phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, triphenylenyl, fluorenyl, spiro[cyclopentan-1,9'-fluoren]yl and spiro[cyclohexane-1,9'- any aryl selected from the group consisting of [fluoren]yl; or any heteroaryl selected from the group consisting of dibenzofuranyl, dibenzothiophenyl, and carbazolyl,

Here, the aryl or heteroaryl is each independently unsubstituted or substituted with 1 to 5 substituents each independently selected from the group consisting of deuterium, C _1-10 alkyl, and C _6-20 aryl.

More preferably, the aryl or heteroaryl is each independently unsubstituted or substituted with 1 to 5 substituents each independently selected from the group consisting of deuterium, methyl, and phenyl.

Most preferably, Ar is any one selected from the group consisting of:

In the above,

Y is O, S, N(phenyl), or C(methyl) ₂ .

Preferably, the compound is represented by any one of the following formulas 1-1 to 1-6:

In Formulas 1-1 to 1-6,

Descriptions of L ₁ to L ₃ , B and Ar are as defined in Formula 1 above,

Q is O or S,

R is hydrogen, phenyl, or naphthyl.

Representative examples of compounds represented by Formula 1 are as follows:

.

Meanwhile, the compound represented by Chemical Formula 1 can be prepared, for example, by a production method as shown in Scheme 1 below. The manufacturing method may be further detailed in the manufacturing examples described later.

[Scheme 1]

In Scheme 1,

Step 1-1 is a step of preparing intermediate compound X (INT. This is the step of preparing the compound represented by Formula 1, which is a tertiary amine compound, by introducing the SM3 radical. Steps 1-1 and 1-2 are both carried out by the Buchwald-Hartwig reaction, and are preferably carried out in the presence of a palladium catalyst. This manufacturing method can be further detailed in the manufacturing examples described later.

organic light emitting device

Meanwhile, the present invention provides an organic light-emitting device containing the compound represented by Formula 1 above. In one example, the present invention includes a first electrode; a second electrode provided opposite to the first electrode; And an organic light-emitting device comprising one or more organic material layers provided between the first electrode and the second electrode, wherein one or more layers of the organic material layers include a compound represented by Formula 1. .

The organic material layer of the organic light emitting device of the present invention may have a single-layer structure, or may have a multi-layer structure in which two or more organic material layers are stacked. For example, the organic light emitting device of the present invention may have a structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, etc. as an organic material layer. However, the structure of the organic light emitting device is not limited to this and may include fewer organic layers.

In addition, the organic material layer may include a hole injection layer, a hole transport layer, or a layer that simultaneously performs hole injection and transport, and the hole injection layer, the hole transport layer, or a layer that simultaneously performs hole injection and transport is represented by Formula 1 Contains the indicated compounds.

Additionally, the organic layer may include a light-emitting layer, and the light-emitting layer includes the compound represented by Formula 1.

The organic material layer of the organic light emitting device of the present invention may have a single-layer structure, or may have a multi-layer structure in which two or more organic material layers are stacked. For example, the organic light-emitting device of the present invention is an organic material layer that, in addition to the light-emitting layer, further includes a hole injection layer and a hole transport layer between the first electrode and the light-emitting layer, and an electron transport layer and an electron injection layer between the light-emitting layer and the second electrode. It can have a structure that does. However, the structure of the organic light emitting device is not limited to this and may include fewer or more organic layers.

In addition, the organic light emitting device according to the present invention is a normal type organic light emitting device in which an anode, one or more organic material layers, and a cathode are sequentially stacked on a substrate where the first electrode is an anode and the second electrode is a cathode. It may be a device. In addition, the organic light emitting device according to the present invention is an inverted type organic device in which a cathode, one or more organic material layers, and an anode are sequentially stacked on a substrate where the first electrode is a cathode and the second electrode is an anode. It may be a light emitting device. For example, the structure of an organic light emitting device according to an embodiment of the present invention is illustrated in FIGS. 1 and 2.

Figure 1 shows an example of an organic light emitting device consisting of a substrate 1, an anode 2, a hole transport layer 3, a light emitting layer 4, an electron injection and transport layer 5, and a cathode 6. In this structure, the compound represented by Formula 1 may be included in the hole transport layer.

Figure 2 shows the substrate (1), anode (2), hole injection layer (7), hole transport layer (3), hole control layer (8), light emitting layer (4), electron control layer (9), electron injection and transport layer ( 5) and a cathode 6. An example of an organic light-emitting device is shown. In this structure, the compound represented by Formula 1 may be included in the hole transport layer, the hole control layer, or both the hole transport layer and the hole control layer.

The organic light emitting device according to the present invention can be manufactured using materials and methods known in the art, except that at least one of the organic layers includes the compound represented by Chemical Formula 1. Additionally, when the organic light emitting device includes a plurality of organic material layers, the organic material layers may be formed of the same material or different materials.

For example, the organic light emitting device according to the present invention can be manufactured by sequentially stacking a first electrode, an organic material layer, and a second electrode on a substrate. At this time, a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation is used to deposit a metal or a conductive metal oxide or an alloy thereof on the substrate to form an anode. It can be manufactured by forming an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer thereon, and then depositing a material that can be used as a cathode thereon. In addition to this method, an organic light-emitting device can be made by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate.

Additionally, the compound represented by Formula 1 may be formed as an organic layer by a solution coating method as well as a vacuum deposition method when manufacturing an organic light-emitting device. Here, the solution application method refers to spin coating, dip coating, doctor blading, inkjet printing, screen printing, spraying, roll coating, etc., but is not limited to these.

In addition to this method, an organic light-emitting device can be manufactured by sequentially depositing a cathode material, an organic layer, and an anode material on a substrate (WO 2003/012890). However, the manufacturing method is not limited to this.

In one example, the first electrode is an anode and the second electrode is a cathode, or the first electrode is a cathode and the second electrode is an anode.

The anode material is generally preferably a material with a large work function to facilitate hole injection into the organic layer. Specific examples of the anode material 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); Combinations of metals and oxides such as ZnO:Al or SNO ₂ :Sb; Conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene](PEDOT), polypyrrole, and polyaniline are included, but are not limited to these.

The cathode material is generally preferably a material with a small work function to facilitate electron injection into the organic 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-layer structure materials such as LiF/Al or LiO ₂ /Al, but they are not limited to these.

The hole injection layer is a layer that injects holes from an electrode. The hole injection material has the ability to transport holes, has an excellent hole injection effect at the anode, a light-emitting layer or a light-emitting material, and has an excellent hole injection effect on the light-emitting layer or light-emitting material. A compound that prevents movement of excitons to the electron injection layer or electron injection material and has excellent thin film forming ability is preferred. It is preferable that the highest occupied molecular orbital (HOMO) of the hole injection material is between the work function of the anode material and the HOMO of the surrounding organic material layer. Specific examples of hole injection materials include metal porphyrin, oligothiophene, arylamine-based organic substances, hexanitrilehexaazatriphenylene-based organic substances, quinacridone-based organic substances, and perylene-based organic substances. These include organic materials, anthraquinone, polyaniline, and polythiophene-based conductive polymers, but are not limited to these.

The hole transport layer is a layer that receives holes from the hole injection layer and transports holes to the light-emitting layer. The hole transport material is a material that can receive holes from the anode or hole injection layer and transfer them to the light-emitting layer, and has high mobility for holes. The material is suitable. As the hole transport material, a compound represented by Formula 1 may be used, or an arylamine-based organic material, a conductive polymer, and a block copolymer having both a conjugated and non-conjugated portion may be used, but is not limited thereto. .

The hole control layer is formed on the hole transport layer, preferably in contact with the light emitting layer, to control hole mobility and prevent excessive movement of electrons to increase the probability of hole-electron coupling, thereby increasing the efficiency of the organic light emitting device. This refers to the layer that plays a role in improving. The hole control layer includes a hole control material, and examples of the hole control material include the compound represented by Chemical Formula 1, or an arylamine-based organic material, but are not limited thereto.

The light-emitting material is a material capable of emitting light in the visible range by receiving and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, and is preferably a material with good quantum efficiency for fluorescence or phosphorescence. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq ₃ ); Carbazole-based compounds; dimerized styryl compounds; BAlq; 10-hydroxybenzoquinoline-metal compound; Compounds of the benzoxazole, benzthiazole and benzimidazole series; Poly(p-phenylenevinylene) (PPV) series polymer; Spiro compounds; Polyfluorene, rubrene, etc., but are not limited thereto.

The light emitting layer may include a host material and a dopant material as described above. The host material may further include a condensed aromatic ring derivative or a heterocyclic ring-containing 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, and ladder-type compounds. These include, but are not limited to, furan compounds and pyrimidine derivatives.

Dopant materials include aromatic amine derivatives, strylamine compounds, boron complexes, fluoranthene compounds, and metal complexes. Specifically, aromatic amine derivatives include condensed aromatic ring derivatives having a substituted or unsubstituted arylamino group, such as pyrene, anthracene, chrysene, and periplanthene, and styrylamine compounds include substituted or unsubstituted arylamino groups. It is a compound in which at least one arylvinyl group is substituted on the arylamine, and is substituted or unsubstituted with one or two or more substituents selected from the group consisting of aryl group, silyl group, alkyl group, cycloalkyl group, and arylamino group. Specifically, styrylamine, styryldiamine, styryltriamine, styryltetraamine, etc. are included, but are not limited thereto. Additionally, metal complexes include, but are not limited to, iridium complexes and platinum complexes.

The electron control layer is formed on the light-emitting layer, preferably in contact with the light-emitting layer, to improve the efficiency of the organic light-emitting device by controlling electron mobility and preventing excessive movement of holes to increase the probability of hole-electron coupling. It refers to the layer that plays a role. The electron control layer contains an electron control material. Examples of the electron control material include azine derivatives including triazine; triazole derivatives; Oxadiazole derivatives; phenanthroline derivatives; Compounds into which electron-withdrawing groups are introduced, such as phosphine oxide derivatives, can be used, but are not limited thereto.

The electron injection and transport layer is a layer that simultaneously functions as an electron transport layer and an electron injection layer for injecting electrons from an electrode and transporting the received electrons to the light-emitting layer, and is formed on the light-emitting layer or the electron control layer. As such an electron injection and transport material, a material that can easily inject electrons from the cathode and transfer them to the light emitting layer, and a material with high mobility for electrons, is suitable. Specific examples of electron injection and transport materials include Al complex of 8-hydroxyquinoline; Complex containing Alq ₃ ; organic radical compounds; hydroxyflavone-metal complex; Triazine derivatives, etc., but are not limited to these. or fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone, etc. and their derivatives, metal complex compounds. , or a nitrogen-containing 5-membered ring derivative, etc., but is not limited thereto.

Examples of the metal complex compounds include 8-hydroxyquinolinato lithium, bis(8-hydroxyquinolinato)zinc, bis(8-hydroxyquinolinato)copper, bis(8-hydroxyquinolinato)manganese, Tris(8-hydroxyquinolinato)aluminum, Tris(2-methyl-8-hydroxyquinolinato)aluminum, Tris(8-hydroxyquinolinato)gallium, bis(10-hydroxybenzo[h] Quinolinato)beryllium, bis(10-hydroxybenzo[h]quinolinato)zinc, bis(2-methyl-8-quinolinato)chlorogallium, bis(2-methyl-8-quinolinato)( o-cresolato) gallium, bis(2-methyl-8-quinolinato)(1-naphtolato) aluminum, bis(2-methyl-8-quinolinato)(2-naphtolato) gallium, etc. It is not limited to this.

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

Additionally, the compound represented by Formula 1 may be included in organic solar cells or organic transistors in addition to organic light-emitting devices.

The preparation of the compound represented by Formula 1 and an organic light-emitting device containing the same will be described in detail in the following Examples. However, the following examples are for illustrating the present invention, and the scope of the present invention is not limited thereto.

Synthesis Example 1: Preparation of substituents

In order to introduce a substituent represented by Formula 2 into the compound represented by Formula 1, intermediate compounds INT.(b1), INT.(b2) and INT are prepared according to Schemes 2-1, 2-2 and 2-3 below. .(b3) Each was prepared.

[Reaction Scheme 2-1]

In Scheme 2-1, X' is halogen, and the description of the remaining substituents is the same as previously described. Step 2-1a is a step of introducing a bromo group into the starting material SM1(b1), and step 2-1b is a step of preparing an intermediate compound INT.(b1) by introducing a linker through a Suzuki coupling reaction. However, if L ₂ is a single bond, step 2-1b can be omitted. The specific manufacturing method is as follows.

1) Step 2-1a: Preparation of intermediate compound SM2(b1)

SM1(b1) (1 eq) was dissolved in THF (excess), the temperature was lowered to -78 degrees, 2.5M n-BuLi (1 eq) was added dropwise, stirred for 3 hours, and N-bromosuccinimide (1 eq) was dissolved in THF (excess). eq) was added. Afterwards, the reactant was warmed to room temperature, stirred for 10 hours, and 1N HCl (excess) was added to terminate the reaction. After completion of the reaction, the layers were separated and the solvent was removed, and the residue was subjected to silica column chromatography (ethyl acetate/hexane 1:15) to prepare the title compound.

2) Step 2-1b: Preparation of intermediate compound INT.(b1)

SM2(b1) (1 eq) and SM3 (1.02 eq) were added to tetrahydrofuran (excess), then 2M potassium carbonate aqueous solution (30 volume ratio compared to THF) was added, and tetrakistriphenyl-phosphinopalladium (2 mol %) was added, and then heated and stirred for 10 hours. After lowering the temperature to room temperature and completing the reaction, the potassium carbonate aqueous solution was removed and the layers were separated. After removing the solvent, it was vacuum distilled and recrystallized from ethyl acetate and hexane to obtain the title compound.

[Reaction Scheme 2-2]

In Scheme 2-2, X' is halogen, and the description of the remaining substituents is the same as previously described. Step 2-2a is a step of introducing a bromo group into the starting material SM1(b2), and step 2-2b is a step of preparing an intermediate compound INT.(b2) by introducing a linker through a Suzuki coupling reaction. However, if L ₂ is a single bond, step 2-2b can be omitted. The specific manufacturing method is as follows:

1) Step 2-2a: Preparation of intermediate compound SM2 (b2)

SM1(b2) (1 eq) was dissolved in DMF (excess), the temperature was lowered to 0 degrees, and after stabilizing the temperature, N-bromosuccinimide (1 eq) was added. Afterwards, the reactant was warmed to room temperature, stirred for 1 hour, and 1N HCl (excess) was added to terminate the reaction. After completion of the reaction, the layers were separated and the solvent was removed, and the residue was subjected to silica column chromatography (ethyl acetate/hexane 1:15) to obtain the title compound.

2) Step 2-2b: Preparation of intermediate compound INT.(b2)

The title compound was obtained in the same manner as step 2-1b, except that SM2(b2) was used instead of SM2(b1) as the starting material in step 2-1b.

[Scheme 2-3]

In Scheme 2-3, X' is halogen, and the description of the remaining substituents is the same as previously described. Step 2-3 is a step of preparing the intermediate compound INT.(b3) by introducing a linker through Suzuki coupling reaction. At this time, the starting material SM1 (b3) is described in the journal “Potent and selective non-benzodioxole-containing endothelin-A receptor antagonists (Journal of Medicinal Chemistry, 1997, vol. 40, # 3, p.322 - 330)” and “Zeolite- It can be prepared by a method known in “catalyzed synthesis of 2, 3-unsubstituted benzo [b] furans via the intramolecular cyclization of 2-aryloxyacetaldehyde acetals (Tetrahedron, 2015, vol. 71, # 29, p.4835 - 4841),” etc. If L ₂ is a single bond, steps 2-3 can be omitted. The specific manufacturing method is as follows.

1) Step 2-3: Preparation of intermediate compound INT.(b3)

The title compound was obtained in the same manner as step 2-1b, except that SM1 (b3) was used instead of SM2 (b1) as the starting material in step 2-1b.

The intermediate compounds shown in Table 1 below were obtained using the methods of Schemes 2-1 to 2-3, and their respective yields and MS data are as follows.

intermediate
compound Starting material 1 Starting material 2 product structure transference number
(%) M.S.
[M+H] ⁺ A4 1.n-BuLi
2. NBS 85% 274.13 B1 NBS, DMF 87% 350.23 B6 NBS, DMF 84% 324.19 C2 88% 305.77 C4 89% 305.77 C5 90% 355.83 C7 88% 381.87 C8 83% 397.93 D2 88% 397.93 D5 85% 305.77 D6 88% 381.87 D7 87% 229.68 D8 81% 335.82 E2 83% 245.74 E3 88% 229.68 E5 84% 229.68 E6 87% 229.68

Synthesis example 2: Preparation of compounds 1 to 21 represented by Formula 1

The compound represented by Formula 1 was prepared according to Scheme 1 below.

[Scheme 1]

In Scheme 1, X' is each independently halogen, preferably bromo or chloro, and the definitions of the remaining substituents are the same as previously described. The specific manufacturing method is as follows.

1) Step 1-1: Intermediate Compound INT. Preparation of X (X1 to X21)

SM1 (1 eq), SM2 (1.02 eq), and sodium-tert-butoxide (1.4 eq) were added to xylene, heated and stirred, refluxed, and [bis(tri-tert-butylphosphine)]palladium (1 mol%) ) was added. After lowering the temperature to room temperature and terminating the reaction, recrystallization was performed using tetrahydrofuran and ethyl acetate to obtain intermediate compounds X1 to

intermediate compound
X SM1 SM2 product structure transference number
(%) M.S.
[M+H] ⁺ X1 78% 346.45 X2 77% 422.54 X3 71% 351.48 X4 76% 522.66 X5 74% 511.64 X6 79% 472.60 X7 70% 396.51 X8 80% 538.71 X9 85% 320.41 X10 84% 396.51 X11 81% 480.64 X12 78% 412.50 X13 80% 488.60 X14 79% 386.47 X15 80% 412.50 X16 83% 336.41 X17 71% 452.59 X18 75% 352.47 X19 76% 256.37 X20 83% 402.53 X21 78% 428.57

2) Step 1-2: Preparation of final compounds 1 to 21

Intermediate Compound INT. X (1 eq), SM3 (1.02 eq), and sodium-tert-butoxide (1.4 eq) were added to xylene, heated and stirred, refluxed, and [bis(tri-tert-butylphosphine)]palladium (1 mol%) ) was added. Afterwards, the temperature was lowered to room temperature and the reaction was terminated, and then recrystallized using tetrahydrofuran and ethyl acetate to obtain the final compounds 1 to 21 below, and the respective yields and MS data are as shown in Table 3.

final
compound intermediate compound
X SM3 transference number
(%) M.S.
[M+H] ⁺ Compound 1 X1 B1 68% 614.76 compound 2 X2 D5 65% 690.86 Compound 3 X3 D2 67% 711.95 Compound 4 X4 A4 84% 714.88 Compound 5 X5 E3 70% 703.86 Compound 6 X6 A4 64% 664.82 Compound 7 X7 C4 68% 664.82 Compound 8 X8 78% 682.88 Compound 9 X9 C5 77% 638.78 Compound 10 X10 C4 74% 664.82 Compound 11 X11 D6 69% 825.05 Compound 12 X12 64% 570.70 Compound 13 X13 D7 67% 680.82 Compound 14 X14 D5 68% 654.78 Compound 15 X15 E2 64% 620.78 Compound 16 X16 D8 78% 634.77 Compound 17 X17 E5 75% 644.80 Compound 18 X18 B6 68% 594.74 Compound 19 X19 C7 72% 620.78 Compound 20 X20 E6 70% 594.74 Compound 21 X21 C8 69% 789.04

Synthesis example 3: Preparation of compound 22 represented by formula 1

The final compound 22 represented by Formula 1 and having the same substituents *-L ₂ -B and *-L ₃ -Ar was prepared according to Scheme 1' below.

[Scheme 1']

In Scheme 1', X' is halogen, preferably bromo or chloro, and the definitions of the remaining substituents are the same as previously described. Specifically, the final compound 22 was obtained by proceeding in the same manner as step 1-1 of Synthesis Example 2, and the yield and MS data are as shown in Table 4.

final
compound SM1 SM2 transference number
(%) M.S.
[M+H] ⁺ Compound 22 D5 68% 806.98

Example One: OLED's manufacturing

A glass substrate (corning 7059 glass) coated with a thin film of ITO (indium tin oxide) to a thickness of 1,000 Å was placed in distilled water with a dispersant dissolved in it and washed ultrasonically. Detergent was used from Fischer Co., and distilled water was from Millipore Co. Distilled water that was filtered secondarily was used as a filter for the product. After washing the ITO for 30 minutes, ultrasonic cleaning was repeated twice with distilled water for 10 minutes. After washing with distilled water, it was ultrasonic washed in the order of isopropyl alcohol, acetone, and methanol and dried.

On the ITO transparent electrode prepared in this way, HI-1 (hexanitrile hexaazatriphenylene) was thermally vacuum deposited to a thickness of 500 Å to form a hole injection layer. Compound 1 (900 Å) synthesized in Preparation Example 2 as a hole transport material was vacuum deposited thereon, and then HT2 was vacuum deposited to a film thickness of 50 Å on the hole transport layer to form a hole control layer.

Next, host BH1 and dopant BD1 compound (25:1) were vacuum deposited as a light emitting layer on the hole control layer to a thickness of 300 Å.

Next, the E1 compound (50Å) was deposited to form an electron control layer, and then the E2 compound and LiQ were deposited (300Å) at a 1:1 ratio (wt%) and sequentially thermally vacuum deposited as the electron injection and transport layer. Lithium fluoride (LiF) with a thickness of 12 Å and aluminum with a thickness of 2,000 Å were sequentially deposited on the electron injection and transport layer to form a cathode, thereby manufacturing an organic light-emitting device.

In the above process, the deposition rate of organic materials was maintained at 1 Å/sec, lithium fluoride was maintained at 0.2 Å/sec, and aluminum was maintained at 3 to 7 Å/sec.

Examples 2 to 7 and Comparative Examples 1 to 3

An organic light-emitting device was manufactured in the same manner as Example 1, except that the compounds listed in Table 5 below were used instead of Compound 1 used in the hole transport layer.

The compounds used in the above examples and comparative examples are as follows.

Experimental Example 1

When current was applied to the organic light-emitting devices manufactured in Examples 1 to 7 and Comparative Examples 1 to 3, the voltage, efficiency, color coordinate, and lifespan were measured, and the results are shown in Table 5 below. At this time, T95 refers to the time required for the luminance to decrease from the initial luminance to 95%.

hole transport layer Hole control layer Voltage
(V)
(@20mA/cm ² ) efficiency
(Cd/A)
(@20mA/cm ² ) Color coordinates
(x,y) life span
(T95,h)
(@20mA/cm ² ) Example 1 Compound 1 HT2 3.42 6.71 (0.135, 0.138) 50.2 Example 2 Compound 5 HT2 3.50 6.63 (0.134, 0.137) 51.2 Example 3 Compound 6 HT2 3.41 6.65 (0.135, 0.138) 54.8 Example 4 Compound 7 HT2 3.34 6.75 (0.134, 0.138) 53.2 Example 5 Compound 8 HT2 3.42 6.74 (0.136, 0.139) 50.1 Example 6 Compound 12 HT2 3.42 6.52 (0.135, 0.138) 55.0 Example 7 Compound 19 HT2 3.34 6.48 (0.133, 0.139) 50.0 Comparative Example 1 HT1 HT2 3.82 5.70 (0.134, 0.139) 28.1 Comparative Example 2 HT3 HT2 3.94 5.81 (0.135, 0.138) 21.8 Comparative Example 3 HT4 HT2 3.78 5.66 (0.134, 0.138) 34.5

As shown in Table 5, the organic light-emitting device using the compound of the present invention as a hole transport layer material is a comparative example compound through smooth hole injection into the light-emitting layer and the balance of holes and electrons in the organic light-emitting device according to the chemical structure. It can be confirmed that it exhibits excellent characteristics in terms of driving voltage, efficiency, and lifespan compared to the organic light-emitting device used as the hole transport layer material.

Example 8: Preparation of OLED

A glass substrate (corning 7059 glass) coated with a thin film of ITO (indium tin oxide) to a thickness of 1,000 Å was placed in distilled water with a dispersant dissolved in it and washed ultrasonically. Detergent was used from Fischer Co., and distilled water was from Millipore Co. Distilled water that was filtered secondarily was used as a filter for the product. After washing the ITO for 30 minutes, ultrasonic cleaning was repeated twice with distilled water for 10 minutes. After washing with distilled water, it was ultrasonic washed in the order of isopropyl alcohol, acetone, and methanol and dried.

On the ITO transparent electrode prepared in this way, HI-1 (hexanitrile hexaazatriphenylene) was thermally vacuum deposited to a thickness of 500 Å to form a hole injection layer. HT1 (900Å), a material that transports holes, was vacuum deposited thereon, and then Compound 2 synthesized in Preparation Example 2 was vacuum deposited on the hole transport layer to a film thickness of 50Å to form a hole control layer.

Next, host BH1 and dopant BD1 compound (25:1) were vacuum deposited as a light emitting layer on the hole control layer to a thickness of 300 Å.

Next, the E1 compound (50 Å) was deposited to form an electron control layer, and then the E2 compound and LiQ were deposited (300 Å) at a 1:1 ratio (wt%) and sequentially thermally vacuum deposited as the electron injection and transport layer. Lithium fluoride (LiF) with a thickness of 12 Å and aluminum with a thickness of 2,000 Å were sequentially deposited on the electron injection and transport layer to form a cathode, thereby manufacturing an organic light-emitting device.

In the above process, the deposition rate of organic materials was maintained at 1 Å/sec, lithium fluoride was maintained at 0.2 Å/sec, and aluminum was maintained at 3 to 7 Å/sec.

Examples 9 to 29 and Comparative Examples 4 to 7

An organic light-emitting device was manufactured in the same manner as Example 8, except that the compounds listed in Table 6 below were used instead of compound HT1 used in the hole transport layer and compound 2 used in the hole control layer.

Experimental Example 2

When current was applied to the organic light-emitting devices manufactured in Examples 8 to 29 and Comparative Examples 4 to 7, the voltage, efficiency, color coordinate, and lifespan were measured, and the results are shown in Table 6 below. At this time, T95 refers to the time required for the luminance to decrease from the initial luminance to 95%.

hole transport layer Hole control layer Voltage (V)
(@20mA/cm ² ) efficiency
(Cd/A)
(@20mA/cm ² ) Color coordinates
(x,y) life span
(T95,h)
(@20mA/cm ² ) Example 8 HT1 Compound 2 3.46 6.78 (0.135, 0.138) 53.0 Example 9 HT1 Compound 3 3.45 6.88 (0.134, 0.138) 55.0 Example 10 HT1 Compound 4 3.52 6.78 (0.134, 0.138) 51.0 Example 11 HT1 Compound 9 3.51 6.77 (0.137, 0.134) 54.0 Example 12 HT1 Compound 10 3.55 6.58 (0.138, 0.138) 55.0 Example 13 HT1 Compound 11 3.38 6.78 (0.135, 0.139) 58.0 Example 14 HT1 Compound 13 3.42 6.78 (0.135, 0.138) 53.0 Example 15 HT1 Compound 14 3.44 6.68 (0.135, 0.139) 60.0 Example 16 HT1 Compound 15 3.41 6.91 (0.134, 0.138) 58.0 Example 17 HT1 Compound 16 3.48 6.88 (0.134, 0.138) 54.0 Example 18 HT1 Compound 17 3.50 6.82 (0.135, 0.139) 54.4 Example 19 HT1 Compound 18 3.38 6.81 (0.135, 0.138) 55.2 Example 20 HT1 Compound 20 3.42 6.78 (0.135, 0.139) 50.2 Example 21 HT1 Compound 21 3.48 6.77 (0.134, 0.138) 50.8 Example 22 Compound 1 Compound 4 3.39 6.71 (0.134, 0.138) 54.4 Example 23 Compound 5 Compound 18 3.48 6.65 (0.135, 0.139) 52.8 Example 24 Compound 6 Compound 15 3.42 6.66 (0.135, 0.138) 53.6 Example 25 Compound 7 Compound 16 3.46 6.78 (0.135, 0.139) 55.0 Example 26 Compound 8 Compound 21 3.44 6.87 (0.134, 0.138) 57.8 Example 27 Compound 12 Compound 9 3.51 6.77 (0.134, 0.138) 54.8 Example 28 Compound 19 Compound 3 3.58 6.81 (0.134, 0.138) 55.0 Example 29 Compound 17 Compound 20 3.55 6.83 (0.134, 0.138) 54.0 Comparative Example 4 HT1 HT5 3.82 5.23 (0.134, 0.138) 38.2 Comparative Example 5 HT1 HT6 3.80 5.33 (0.137, 0.135) 30.2 Comparative Example 6 HT3 HT5 3.77 5.48 (0.134, 0.138) 33.4 Comparative Example 7 HT4 HT6 3.72 5.78 (0.135, 0.137) 32.5

As shown in Table 6, the organic light-emitting device using the compound of the present invention as a hole control layer material or a hole control layer material and a hole transport layer material simultaneously has smooth hole injection into the light-emitting layer and hole injection of the organic light-emitting device according to the chemical structure. Through the balance of and electrons, it can be confirmed that it exhibits excellent characteristics in terms of driving voltage, efficiency, and lifespan compared to the organic light-emitting device using the comparative example compound.

1: Substrate 2: Anode
3: hole transport layer 4: light emitting layer
5: Electron injection and transport layer 6: Cathode
7: hole injection layer 8: hole control layer
9: Electronic control layer

Claims (9)

Compound represented by Formula 1:
[Formula 1]

In Formula 1,
L ₁ and L ₃ are each independently a single bond; or C _6-60 arylene substituted or unsubstituted with deuterium,
L ₂ is each independently a single bond, phenylene, or naphthylene,
A is dibenzofuranyl, or dibenzothiophenyl,
Here, A is unsubstituted or substituted with one or more C _6-20 aryl,
B is a substituent represented by the following formula 2,
Ar is phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, triphenylenyl, spiro[cyclopentan-1,9'-fluoren]yl and spiro[cyclohexane-1,9'-fluorene. ] is any aryl selected from the group consisting of
Here, aryl in Ar is unsubstituted or substituted with 1 to 5 substituents each independently selected from the group consisting of deuterium, C _1-10 alkyl, and C _6-20 aryl,
[Formula 2]

In Formula 2,
X is O or S,
One of R ₁ and R ₃ is bonded to L ₂ and the other is hydrogen; heavy hydrogen; C _1-60 alkyl substituted or unsubstituted with deuterium; C _6-60 aryl substituted or unsubstituted with deuterium; or C _2-60 heteroaryl containing any one heteroatom selected from the group consisting of O and S substituted or unsubstituted with deuterium,
R ₂ is hydrogen; heavy hydrogen; C _1-60 alkyl substituted or unsubstituted with deuterium; or C _6-60 aryl substituted or unsubstituted with deuterium,
However, when L ₂ is combined with R ₁ , R ₂ is not hydrogen,
n is an integer from 1 to 4.
According to paragraph 1,
L ₁ and L ₃ are each independently a single bond, phenylene, biphenyldiyl, or naphthylene,
compound.
According to paragraph 1,
A is represented by the formula a3 or a4,
compound:

In the above formulas a3 and a4,
Each R is independently hydrogen, or C _6-20 aryl.
According to paragraph 1,
The substituent represented by Formula 2 is represented by the formula b1 or b3 below,
compound:

In the above formulas b1 and b3,
X is O or S,
R ₂ is C _1-10 alkyl, or C _6-20 aryl,
R ₁ 'is hydrogen, C _1-10 alkyl, C _6-20 aryl, or C _2-20 heteroaryl containing heteroatoms O or S,
R ₃ , R ₂ ' and R ₃ ' are each independently hydrogen, C _1-10 alkyl, or C _6-20 aryl.
According to paragraph 4,
According to claim 4 of formula b,
In the above formula b1,
R ₂ is methyl, ethyl, phenyl, or biphenylyl,
R ₃ is hydrogen, methyl, or phenyl,
In formula b3,
R ₁ 'is hydrogen, methyl, isopropyl, naphthyl, phenyl, or dibenzothiophenyl,
R ₂ ' and R ₃ ' are each independently hydrogen, methyl, isopropyl, naphthyl, or phenyl,
compound.
According to paragraph 1,
Ar is any one selected from the group consisting of:
compound:

.
According to paragraph 1,
The compound is represented by any one of the following formulas 1-4 to 1-6,
compound:

In Formulas 1-4 to 1-6,
The descriptions of L ₁ to L ₃ , B and Ar are as defined in paragraph 1,
Q is O or S,
R is hydrogen, phenyl, or naphthyl.
According to paragraph 1,
The compound is any one selected from the group consisting of the following compounds:



.
first electrode; a second electrode provided opposite to the first electrode; And an organic light-emitting device comprising at least one organic material layer provided between the first electrode and the second electrode, wherein at least one layer of the organic material layer includes the compound according to any one of claims 1 to 8. And, the organic material layer containing the compound is a hole transport layer or a hole control layer.