KR20230108602A - Novel compound and organic light emitting device comprising the same - Google Patents

Abstract

The present invention relates to a novel compound represented by chemical formula 1 and to an organic light-emitting device comprising the same. The compound improves efficiency, and has low driving voltage and/or lifespan characteristics in the organic light-emitting device.

Description

Novel compound and organic light emitting device including the same

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

In general, the organic light emitting phenomenon refers to a phenomenon in which electrical energy is converted into light energy using an organic material. An organic light emitting device using an organic light emitting phenomenon has a wide viewing angle, excellent contrast, and a fast response time, and has excellent luminance, driving voltage, and response speed characteristics, and thus many studies are being conducted.

An organic light emitting device generally has a structure including an anode, a cathode, and an organic material layer between the anode and the cathode. In order to increase the efficiency and stability of the organic light emitting device, the organic material layer is often composed of a multi-layered structure composed of different materials, and may include, 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 are injected into the organic material layer, and when the injected holes and electrons meet, excitons are formed. When it falls back to the ground state, it glows.

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

Meanwhile, in recent years, an organic light emitting device using a solution process, particularly an inkjet process, instead of a conventional deposition process has been developed to reduce process costs. In the early days, an attempt was made to develop an organic light emitting device by coating all organic light emitting device layers with a solution process, but current technology has limitations, so only HIL, HTL, and EML are processed as a solution process, and the subsequent process is a hybrid that utilizes the existing deposition process. (hybrid) process is under investigation.

Accordingly, the present invention provides a novel organic light emitting device material that can be used in an organic light emitting device and can be used in a solution process at the same time.

Korean Patent Publication No. 10-2000-0051826

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

The present invention provides a compound represented by Formula 1 below:

[Formula 1]

In Formula 1,

A is each independently a substituted or unsubstituted C _3-10 cycloalkane ring fused with an adjacent ring,

R ₁ to R ₄ are each independently hydrogen, deuterium, or substituted or unsubstituted C _1-60 alkyl, or two adjacent R ₁ to R ₄ are bonded to each other to be substituted or unsubstituted C _6-60 form an aryl;

R ₅ are each independently hydrogen, deuterium, or substituted or unsubstituted C _1-60 alkyl;

R ₆ are each independently hydrogen, deuterium, or substituted or unsubstituted C _1-60 alkyl;

R' ₁ and R' ₂ are each independently hydrogen, deuterium, or substituted or unsubstituted C _1-60 alkyl;

a, b, c, and d are each independently an integer from 2 to 16;

n is an integer from 1 to 10;

In addition, 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 represented by Chemical Formula 1. .

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

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

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

(Definition of Terms)

In this specification, or means a bond connected to another substituent.

In this specification, the term "substituted or unsubstituted" means deuterium; halogen group; nitrile group; nitro group; hydroxy group; carbonyl group; ester group; imide group; amino group; phosphine oxide group; alkoxy group; aryloxy group; Alkyl thioxy group; Arylthioxy group; an alkyl sulfoxy group; aryl sulfoxy group; silyl group; boron group; an alkyl group; cycloalkyl group; alkenyl group; aryl group; aralkyl group; Aralkenyl group; Alkyl aryl 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 a heterocyclic group containing at least one of N, O, and S atoms, or substituted or unsubstituted with two or more substituents linked to each other among the substituents exemplified above. . For example, "a substituent in which two or more substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group, and may be interpreted as a substituent in which two phenyl groups are connected.

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

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

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

In the present specification, the silyl group is specifically a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, a phenylsilyl group, and the like. but not limited to

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

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

In the present specification, the alkyl group may be straight-chain or branched-chain, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to one embodiment, the number of carbon atoms of the alkyl group is 1 to 20. According to another exemplary embodiment, the number of carbon atoms of the alkyl group is 1 to 10. According to another exemplary embodiment, the alkyl group has 1 to 6 carbon atoms. Specific examples of the alkyl group 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 thereto.

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

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and according to an exemplary embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another exemplary embodiment, the number of carbon atoms of the cycloalkyl group is 3 to 20. According to another exemplary embodiment, the number of carbon atoms 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, 4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like, but are not limited thereto.

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 number of carbon atoms of the aryl group is 6 to 30. According to one embodiment, the number of carbon atoms of the aryl group is 6 to 20. The aryl group may be a phenyl group, a biphenyl group, a terphenyl group, etc. as a monocyclic aryl group, but is not limited thereto. The polycyclic aryl group may be a naphthyl group, anthracenyl group, phenanthryl group, pyrenyl group, perylenyl group, chrysenyl group, 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. When the fluorenyl group is substituted, etc. However, it is not limited thereto.

In the present specification, the heterocyclic group is a heterocyclic group containing at least one of O, N, Si, and S as heterogeneous elements, and the number of carbon atoms is not particularly limited, but preferably has 2 to 60 carbon atoms. Examples of the heterocyclic group include a thiophene group, a furan group, a pyrrole group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a triazole group, a pyridyl group, a bipyridyl group, a pyrimidyl group, a triazine group, and an acridyl group. , pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyridopyrimidinyl group, pyridopyrazinyl group, pyrazinopyrazinyl group, isoquinoline group, indole group , carbazole group, benzoxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group, isoxazolyl group, thiadia A zolyl group, a phenothiazinyl group, and a dibenzofuranyl group, but are not limited thereto.

In the present specification, an aralkyl group, an aralkenyl group, an alkylaryl group, and an aryl group among arylamine groups are the same as the examples of the aryl group described above. In the present specification, the alkyl group among the aralkyl group, the alkylaryl group, and the alkylamine group is the same as the examples of the above-mentioned alkyl group. In the present specification, the description of the heterocyclic group described above may be applied to the heteroaryl of the heteroarylamine. In the present specification, the alkenyl group among the aralkenyl groups is the same as the examples of the alkenyl group described above. In the present specification, the description of the aryl group described above may be applied except that the arylene is a divalent group. In the present specification, the description of the heterocyclic group described above may be applied except that the heteroarylene is a divalent group. In the present specification, the hydrocarbon ring is not a monovalent group, and the description of the aryl group or cycloalkyl group described above may be applied, except that the hydrocarbon ring is formed by combining two substituents. In the present specification, the heterocyclic group is not a monovalent group, and the description of the above-described heterocyclic group may be applied, except that it is formed by combining two substituents.

(compound)

The present invention provides a compound represented by Formula 1 above.

Preferably, each A is independently a substituted or unsubstituted cyclopentane or cyclohexane ring fused with an adjacent ring.

Preferably, R ₁ to R ₄ are each independently hydrogen, deuterium, or methyl, or two adjacent R ₁ to R ₄ combine with each other to form substituted or unsubstituted benzene.

Preferably, Formula 1 is represented by any one selected from the group consisting of the following Formulas 1-1 to 1-16:

In Formulas 1-1 to 1-16,

R ₅ , R ₆ , R' ₁ , R' ₂ , and n are as previously defined.

Preferably, R ₅ and R ₆ are each independently hydrogen, deuterium, or methyl.

Preferably, R' ₁ and R' ₂ are each independently hydrogen, deuterium, methyl, isopropyl, or tertbutyl.

Preferably, n is an integer from 2 to 5.

Representative examples of the compound represented by Formula 1 are as follows:

On the other hand, the present invention provides a method for producing a compound represented by Formula 1, such as the following Reaction Scheme 1, for example:

[Scheme 1]

In the reaction scheme, other definitions except for Y are as defined above, and Y is halogen, preferably bromo or chloro.

Meanwhile, the organic layer containing the compound according to the present invention can be formed using various methods such as a vacuum deposition method and a solution process, and the solution process will be described in detail below.

(coating composition)

Meanwhile, the compound according to the present invention may form an organic material layer of an organic light emitting device, particularly a light emitting layer, through a solution process. Specifically, the compound may be used as a dopant material of the light emitting layer. To this end, the present invention provides a coating composition comprising the above-described compound and a solvent according to the present invention.

The solvent is not particularly limited as long as it can dissolve or disperse the compound according to the present invention, and examples thereof include chloroform, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, chlorobenzene, o -Chlorinated solvents such as dichlorobenzene; ether solvents such as tetrahydrofuran and dioxane; aromatic hydrocarbon solvents such as toluene, xylene, trimethylbenzene, and mesitylene; aliphatic hydrocarbon-based solvents such as cyclohexane, methylcyclohexane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane, and n-decane; Ketone solvents, such as acetone, methyl ethyl ketone, and cyclohexanone; Ester solvents, such as ethyl acetate, butyl acetate, and ethyl cellosolve acetate; Ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, dimethoxyethane, propylene glycol, diethoxymethane, triethylene glycol monoethyl ether, glycerin, 1,2-hexanediol, etc. alcohol and its derivatives; alcohol solvents such as methanol, ethanol, propanol, isopropanol, and cyclohexanol; sulfoxide solvents such as dimethyl sulfoxide; and amide solvents such as N-methyl-2-pyrrolidone and N,N-dimethylformamide; benzoate solvents such as butyl benzoate and methyl-2-methoxy benzoate; tetralin; Solvents, such as 3-phenoxytoluene, are mentioned. In addition, the above-mentioned solvent may be used alone or in combination of two or more solvents. Preferably, toluene may be used as the solvent.

In addition, the coating composition may further include a compound used as a host material, and a description of the compound used for the host material will be described later. In addition, the coating composition may include a compound used as a dopant material, and a description of the compound used for the dopant material will be described later.

In addition, the viscosity of the coating composition is preferably 1 cP or more. In addition, considering the ease of coating of the coating composition, the viscosity of the coating composition is preferably 10 cP or less. Also, the concentration of the compound according to the present invention in the coating composition is preferably 0.1 wt/v% or more. In addition, the concentration of the compound according to the present invention in the coating composition is preferably 20 wt / v% or less so that the coating composition can be coated optimally.

In addition, the present invention provides a method of forming a light emitting layer using the coating composition described above. Specifically, coating the light emitting layer according to the present invention described above on the anode or on the hole transport layer formed on the anode by a solution process; and heat-treating the coated coating composition.

The solution process uses the above-described coating composition according to the present invention, and includes spin coating, dip coating, doctor blading, inkjet printing, screen printing, spraying, roll coating, etc., but is not limited thereto.

In the heat treatment step, the heat treatment temperature is preferably 150 to 230 °C. In addition, the heat treatment time is 1 minute to 3 hours, more preferably 10 minutes to 1 hour. In addition, the heat treatment is preferably performed in an inert gas atmosphere such as argon or nitrogen.

(organic light emitting element)

In addition, the present invention provides an organic light emitting device including the compound represented by Formula 1 above. In one example, the present invention provides a first electrode; a second electrode provided to face the first electrode; and an emission layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes the compound represented by Chemical 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, and the like as organic layers. However, the structure of the organic light emitting device is not limited thereto and may include fewer organic layers.

Also, the organic layer may include a light emitting layer, and the light emitting layer includes the compound represented by Chemical Formula 1. In particular, the compound according to the present invention can be used as a dopant of the light emitting layer.

Also, the organic light emitting device according to the present invention may be 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. In addition, the organic light emitting device according to the present invention may be an organic light emitting device of an inverted type in which a cathode, one or more organic material layers, and an anode are sequentially stacked on a substrate. 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 .

1 shows an example of an organic light emitting device composed of a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4. In this structure, the compound represented by Chemical Formula 1 may be included in the light emitting layer.

2 is an example of an organic light emitting device composed of a substrate (1), an anode (2), a hole injection layer (5), a hole transport layer (6), a light emitting layer (7), an electron injection and transport layer (8), and a cathode (4). is shown. In this structure, the compound represented by Chemical Formula 1 may be included in the light emitting layer.

The organic light emitting device according to the present invention may 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. Also, 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 may be manufactured by sequentially stacking an anode, an organic material layer, and a cathode on a substrate. At this time, using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation, depositing a metal or a metal oxide having conductivity or an alloy thereof on the substrate to form an anode After forming an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer thereon, and depositing a material that can be used as a cathode thereon, it can be prepared.

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

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.

As the anode material, a material having a high work function is generally preferred so that holes can be smoothly injected into the organic material layer. Specific examples of the cathode 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 SnO2:Sb; conductive compounds such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), polypyrrole, and polyaniline; and the like, but are not limited thereto.

The cathode material is preferably a material having a small work function so as to easily inject electrons into the organic material layer. Specific examples of the anode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof; There are multi-layered materials such as LiF/Al or LiO ₂ /Al, but are not limited thereto.

The hole injection layer is a layer for injecting holes from the electrode, and the hole injection material has the ability to transport holes and has a hole injection effect at the anode, an excellent hole injection effect for the light emitting layer or the light emitting material, and generated in the light emitting layer A compound that prevents migration of excitons to the electron injecting layer or electron injecting material and has excellent thin film formation 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 layer. Specific examples of the hole injection material include metal porphyrins, oligothiophenes, arylamine-based organic materials, hexanitrilehexaazatriphenylene-based organic materials, quinacridone-based organic materials, and perylene-based organic materials. of organic matter, anthraquinone, and polyaniline and polythiophene-based conductive compounds, but are not limited thereto.

The hole transport layer is a layer that receives holes from the hole injection layer and transports the holes to the light emitting layer. The hole transport material is a material that can receive holes from the anode or the hole injection layer and transfer them to the light emitting layer, and has high hole mobility. material is suitable. Specific examples include, but are not limited to, arylamine-based organic materials, conductive compounds, and block copolymers having both conjugated and non-conjugated parts.

The light emitting layer may include a host material and a dopant material. As the host material, a condensed aromatic ring derivative or a compound containing a heterocyclic ring can be used. Specifically, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, etc., and heterocyclic-containing compounds include carbazole derivatives, dibenzofuran derivatives, ladder type furan compounds, pyrimidine derivatives, etc., but are not limited thereto.

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

The electron injection and transport layer is a layer that simultaneously serves 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 injecting and transporting material, a material capable of receiving electrons from the cathode and transferring them to the light emitting layer is suitable. Examples of specific electron injection and transport materials include Al complexes of 8-hydroxyquinoline; Complexes containing Alq ₃ ; organic radical compounds; hydroxyflavone-metal complexes; triazine derivatives, etc., but are not limited thereto. or LiF, NaF, NaCl, CsF, Li ₂ O, BaO, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, pre Orenylidene methane, anthrone, and the like and derivatives thereof, metal complex compounds, or nitrogen-containing 5-membered ring derivatives may be used, but are not limited thereto.

Examples of the metal complex compound include 8-hydroxyquinolinato lithium, bis(8-hydroxyquinolinato)zinc, bis(8-hydroxyquinolinato)copper, bis(8-hydroxyquinolinato)manganese, Tris(8-hydroxyquinolinato) aluminum, tris(2-methyl-8-hydroxyquinolinato) aluminum, tris(8-hydroxyquinolinato) gallium, bis(10-hydroxybenzo[h] Quinolinato) beryllium, bis(10-hydroxybenzo[h]quinolinato)zinc, bis(2-methyl-8-quinolinato)chlorogallium, bis(2-methyl-8-quinolinato)( There are o-cresolato) gallium, bis(2-methyl-8-quinolinato)(1-naphtolato)aluminum, and bis(2-methyl-8-quinolinato)(2-naphtolato)gallium. Not limited to this.

In addition to the above-described materials, an inorganic compound such as a quantum dot or a polymer compound may be further included in the light emitting layer, the hole injection layer, the hole transport layer, the electron transport layer, and the electron injection layer.

The quantum dot may be, for example, a colloidal quantum dot, an alloy quantum dot, a core-shell quantum dot, or a core quantum dot. An element belonging to groups 2 and 16, an element belonging to groups 13 and 15, an element belonging to groups 13 and 17, an element belonging to groups 11 and 17, or an element belonging to groups 14 and 17 It may be a quantum dot containing elements belonging to group 15, such as cadmium (Cd), selenium (Se), zinc (Zn), sulfur (S), phosphorus (P), indium (In), tellurium (Te), lead Quantum dots including elements such as (Pb), gallium (Ga), and arsenic (As) may be used.

The organic light emitting device according to the present invention may be a bottom emission device, a top emission device, or a double-sided light emitting device, and in particular, may be a bottom emission device requiring relatively high light emitting efficiency.

In addition, the compound according to the present invention may be included in an organic solar cell or an organic transistor in addition to an organic light emitting device.

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

[Example]

Example 1: Preparation of Compound 1

Compound 1-a (1.0 eq.), NaO t -Bu (4 eq.), and compound 1-b (1.05 eq.) were placed in a round bottom flask and dissolved in anhydrous PhMe (0.1 M). Pd( t -Bu ₃ P) ₂ (5 mol%) was added dropwise under a bath temperature of 120 °C and stirred for 2 hours. After the reaction, the reactant was cooled at room temperature, sufficiently diluted with CH ₂ Cl ₂ , washed with CH ₂ Cl ₂ /brine, and the organic layer was separated. Water was removed with MgSO ₄ and passed through a Celite-Florisil-Silica pad. The passed solution was concentrated under reduced pressure and purified by column chromatography to prepare compound 1-c (91% yield).

Compound 1-d (1.0 eq.), NaO t -Bu (4 eq.), and compound 1-c (2.05 eq.) were placed in a round bottom flask and dissolved in anhydrous PhMe (0.1 M). Pd( t -Bu ₃ P) ₂ (5 mol%) was added dropwise under a bath temperature of 120 °C and stirred for 4 hours. After the reaction, the reactant was cooled at room temperature, sufficiently diluted with CH ₂ Cl ₂ , washed with CH ₂ Cl ₂ /brine, and the organic layer was separated. Water was removed with MgSO ₄ and passed through a Celite-Florisil-Silica pad. The passed solution was concentrated under reduced pressure and purified by column chromatography to prepare compound 1-e (83% yield).

Compound 1-e (1.0 eq.), NaO t -Bu (4 eq.), and compound 1-f (1.05 eq.) were placed in a round bottom flask and dissolved in anhydrous PhMe (0.1 M). Pd( t -Bu ₃ P) ₂ (5 mol%) was added dropwise under a bath temperature of 120 °C and stirred overnight. After the reaction, the reactant was cooled at room temperature, sufficiently diluted with CH ₂ Cl ₂ , washed with CH ₂ Cl ₂ /brine, and the organic layer was separated. Water was removed with MgSO ₄ and passed through a Celite-Florisil-Silica pad. The passed solution was concentrated under reduced pressure and purified by column chromatography to prepare compound 1-g (88% yield).

Compound 1-g (1.0 eq.) was placed in a round bottom flask and dissolved in anhydrous PhMe (0.03 M). BI ₃ (2.0 eq.) was slowly added dropwise to the reaction mixture and stirred overnight under a bath temperature of 80 °C. After the reaction, the reactant was sufficiently cooled at room temperature and diluted with CH ₂ Cl ₂ . EtN i -Pr ₂ (15.0 eq.) and sat.Na ₂ S ₂ O ₃ (aq.) were sequentially added dropwise to the reactant, washed with CH ₂ Cl ₂ /H ₂ O, and the organic layer was separated. Water was removed with MgSO ₄ and passed through a Celite-Florisil-Silica pad. The passed solution was concentrated under reduced pressure and purified by column chromatography to prepare Compound 1 (81% yield).

m/z [M+H] ⁺ 944.7

Example 2: Preparation of Compound 2

Compound 2 was prepared in the same manner as in Compound 1, except that Compound 2-a was used instead of Compound 1-f.

m/z [M+H] ⁺ 930.8

Example 3: Preparation of Compound 3

Compound 3 was prepared in the same manner as the method for preparing compound 1, except that compound 3-a was used instead of compound 1-f.

m/z [M+H] ⁺ 958.7

Example 4: Preparation of Compound 4

Compound 4 was prepared in the same manner as the method for preparing compound 1, except that compound 4-a was used instead of compound 1-f.

m/z [M+H] ⁺ 972.8

Example 5: Preparation of Compound 5

Compound 5 was prepared in the same manner as in the preparation method of Compound 1, except that Compound 5-a was used instead of Compound 1-f.

m/z [M+H] ⁺ 1000.8

Example 6: Preparation of Compound 6

Compound 6 was prepared in the same manner as the method for preparing compound 1, except that compound 6-a was used instead of compound 1-f.

m/z [M+H] ⁺ 1056.7

Example 7: Preparation of Compound 7

Compound 7 was prepared in the same manner as in the method for preparing Compound 1, except that Compound 7-a was used instead of Compound 1-a and Compound 7-b was used instead of Compound 1-b.

m/z [M+H] ⁺ 1136.8

Example 8: Preparation of Compound 8

Compound 8 was prepared in the same manner as the method for preparing compound 7, except that compound 2-a was used instead of compound 1-f.

m/z [M+H] ⁺ 1122.5

Example 9: Preparation of compound 9

Compound 9 was prepared in the same manner as the compound 7, except that compound 3-a was used instead of compound 1-f.

m/z [M+H] ⁺ 1150.7

Example 10: Preparation of compound 10

Compound 10 was prepared in the same manner as in Compound 7, except that Compound 4-a was used instead of Compound 1-f.

m/z [M+H] ⁺ 1164.7

Example 11: Preparation of Compound 11

Compound 11 was prepared in the same manner as the method for preparing compound 7, except that compound 5-a was used instead of compound 1-f.

m/z [M+H] ⁺ 1192.8

Example 12: Preparation of compound 12

Compound 12 was prepared in the same manner as in the preparation method of Compound 7, except that Compound 6-a was used instead of Compound 1-f.

m/z [M+H] ⁺ 1248.7

Example 13: Preparation of compound 13

Compound 13 was prepared in the same manner as in the method for preparing Compound 1, except that Compound 13-a was used instead of Compound 1-a and Compound 13-b was used instead of Compound 1-b.

m/z [M+H] ⁺ 944.7

Example 14: Preparation of compound 14

Compound 14 was prepared in the same manner as the method for preparing compound 13, except that compound 3-a was used instead of compound 1-f.

m/z [M+H] ⁺ 958.7

Example 15: Preparation of compound 15

Compound 15 was prepared in the same manner as the method for preparing compound 13, except that compound 5-a was used instead of compound 1-f.

m/z [M+H] ⁺ 1000.8

Example 16: Preparation of compound 16

Compound 16 was prepared in the same manner as in the method for preparing Compound 1, except that Compound 16-a was used instead of Compound 1-a and Compound 16-b was used instead of Compound 1-b.

m/z [M+H] ⁺ 736.6

Example 17: Preparation of compound 17

Compound 17 was prepared in the same manner as the method for preparing compound 16, except that compound 3-a was used instead of compound 1-f.

m/z [M+H] ⁺ 750.8

Example 18: Preparation of compound 18

Compound 18 was prepared in the same manner as the method for preparing compound 16, except that compound 5-a was used instead of compound 1-f.

m/z [M+H] ⁺ 792.5

Example 19: Preparation of compound 19

Compound 19 was prepared in the same manner as in the method for preparing Compound 1, except that Compound 19-a was used instead of Compound 1-a and Compound 19-b was used instead of Compound 1-b.

m/z [M+H] ⁺ 720.3

Example 20: Preparation of compound 20

Compound 20 was prepared in the same manner as the method for preparing compound 19, except that compound 3-a was used instead of compound 1-f.

m/z [M+H] ⁺ 734.7

Example 21: Preparation of compound 21

Compound 21 was prepared in the same manner as in the method for preparing Compound 1, except that Compound 21-a was used instead of Compound 1-a and Compound 21-b was used instead of Compound 1-b.

m/z [M+H] ⁺ 912.6

Example 22: Preparation of compound 22

Compound 22 was prepared in the same manner as the method for preparing compound 21, except that compound 3-a was used instead of compound 1-f.

m/z [M+H] ⁺ 926.6

Example 23: Preparation of compound 23

Compound 23 was prepared in the same manner as in the method for preparing Compound 1, except that Compound 23-a was used instead of Compound 1-a and Compound 23-b was used instead of Compound 1-b.

m/z [M+H] ⁺ 736.6

Example 24: Preparation of compound 24

Compound 24 was prepared in the same manner as the method for preparing compound 23, except that compound 3-a was used instead of compound 1-f.

m/z [M+H] ⁺ 750.8

Example 25: Preparation of compound 25

Compound 25 was prepared in the same manner as in the method for preparing Compound 1, except that Compound 25-a was used instead of Compound 1-a and Compound 25-b was used instead of Compound 1-b.

m/z [M+H] ⁺ 928.7

Example 26: Preparation of compound 26

Compound 26 was prepared in the same manner as in the method for preparing compound 25, except that compound 3-a was used instead of compound 1-f.

m/z [M+H] ⁺ 942.7

Example 27: Preparation of compound 27

Compound 27 was prepared in the same manner as in the method for preparing Compound 1, except that Compound 27-a was used instead of Compound 1-a and Compound 27-b was used instead of Compound 1-b.

m/z [M+H] ⁺ 664.5

Example 28: Preparation of compound 28

Compound 28 was prepared in the same manner as the method for preparing compound 27, except that compound 3-a was used instead of compound 1-f.

m/z [M+H] ⁺ 678.5

Example 29: Preparation of compound 29

Compound 29 was prepared in the same manner as in the method for preparing Compound 1, except that Compound 29-a was used instead of Compound 1-a and Compound 29-b was used instead of Compound 1-b.

m/z [M+H] ⁺ 720.6

Example 30: Preparation of compound 30

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Compound 30 was prepared in the same manner as in the method for preparing compound 29, except that compound 3-a was used instead of compound 1-f.

m/z [M+H] ⁺ 734.6

Example 31: Preparation of Compound 31

Compound 31 was prepared in the same manner as in the method for preparing Compound 1, except that Compound 31-a was used instead of Compound 1-a and Compound 31-b was used instead of Compound 1-b.

m/z [M+H] ⁺ 832.4

Example 32: Preparation of compound 32

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Compound 32 was prepared in the same manner as the method for preparing compound 31, except that compound 3-a was used instead of compound 1-f.

m/z [M+H] ⁺ 846.7

Example 33: Preparation of compound 33

Compound 33 was prepared in the same manner as in the method for preparing Compound 1, except that Compound 33-a was used instead of Compound 1-a and Compound 33-b was used instead of Compound 1-b.

m/z [M+H] ⁺ 776.4

Example 34: Preparation of Compound 34

Compound 34 was prepared in the same manner as the method for preparing compound 33, except that compound 3-a was used instead of compound 1-f.

m/z [M+H] ⁺ 790.2

Example 35: Preparation of compound 35

Compound 35 was prepared in the same manner as in the method for preparing Compound 1, except that Compound 35-a was used instead of Compound 1-a and Compound 35-b was used instead of Compound 1-b.

m/z [M+H] ⁺ 968.6

Example 36: Preparation of compound 36

Compound 36 was prepared in the same manner as the method for preparing compound 35, except that compound 3-a was used instead of compound 1-f.

m/z [M+H] ⁺ 982.5

[Comparative example]

Comparative Example 1: Preparation of Compound F

Compound 1-d (1.0 eq.), NaO t -Bu (4.0 eq.), and compound Fa (2.05 eq.) were placed in a round bottom flask and dissolved in anhydrous PhMe (0.1 M). Pd( t -Bu ₃ P) ₂ (5 mol%) was added dropwise under a bath temperature of 120 °C and stirred overnight. After the reaction, the reactant was cooled at room temperature, sufficiently diluted with CH ₂ Cl ₂ , washed with CH ₂ Cl ₂ /brine, and the organic layer was separated. Water was removed with MgSO ₄ and passed through a Celite-Florisil-Silica pad. The passed solution was concentrated under reduced pressure and purified by column chromatography to prepare compound Fb (75% yield).

Compound Fb (1.0 eq.) was placed in a round bottom flask and dissolved in anhydrous PhMe (0.03 M). BI ₃ (2.0 eq.) was slowly added dropwise to the reaction mixture and stirred overnight under a bath temperature of 80 °C. After the reaction, the reactant was sufficiently cooled at room temperature and diluted with CH ₂ Cl ₂ . EtN i -Pr ₂ (15.0 eq.) and sat.Na ₂ S ₂ O ₃ (aq.) were sequentially added dropwise to the reactant, washed with CH ₂ Cl ₂ /H ₂ O, and the organic layer was separated. Water was removed with MgSO ₄ and passed through a Celite-Florisil-Silica pad. The passed solution was concentrated under reduced pressure and purified by column chromatography to prepare compound F (87% yield).

m/z [M+H] ⁺ = 659.6

Comparative Example 2: Preparation of Compound G

Compound G was prepared in the same manner as in the method for preparing compound F, except that compound G-a was used instead of compound F-a.

m/z [M+H] ⁺ = 659.5

Comparative Example 3: Preparation of Compound H

Compound Ha (1.0 eq.), NaO t -Bu (4.0 eq.), and compound Hb (1.05 eq.) were placed in a round bottom flask and dissolved in anhydrous PhMe (0.1 M). Pd( t -Bu ₃ P) ₂ (5 mol%) was added dropwise under a bath temperature of 120 °C and stirred overnight. After the reaction, the reactant was cooled at room temperature, sufficiently diluted with CH ₂ Cl ₂ , washed with CH ₂ Cl ₂ /brine, and the organic layer was separated. Water was removed with MgSO ₄ and passed through a Celite-Florisil-Silica pad. The passed solution was concentrated under reduced pressure and purified by column chromatography to obtain compound Hc (79% yield).

Compound Hc (1.0 eq.) was placed in a round bottom flask and dissolved in anhydrous PhMe (0.03 M). BI ₃ (2.0 eq.) was slowly added dropwise to the reaction mixture and stirred overnight under a bath temperature of 80 °C. After the reaction, the reactant was sufficiently cooled at room temperature and diluted with CH ₂ Cl ₂ . EtN i -Pr ₂ (15.0 eq.) and sat.Na ₂ S ₂ O ₃ (aq.) were sequentially added dropwise to the reactant, washed with CH ₂ Cl ₂ /H ₂ O, and the organic layer was separated. Water was removed with MgSO ₄ and passed through a Celite-Florisil-Silica pad. The passed solution was concentrated under reduced pressure and purified by column chromatography to obtain compound H (73% yield).

m/z [M+H] ⁺ = 725.5

[Experimental example]

Experimental Example 1

A glass substrate coated with indium tin oxide (ITO) to a thickness of 500 Å was put in distilled water in which detergent was dissolved and washed with ultrasonic waves. At this time, a product of Fischer Co. was used as a detergent, and distilled water filtered through a second filter of a product of Millipore Co. was used as distilled water. After washing the ITO for 30 minutes, ultrasonic cleaning was performed twice with distilled water for 10 minutes. After washing with distilled water, ultrasonic cleaning was performed with solvents such as isopropyl and acetone, and after drying, the substrate was washed for 5 minutes and transported to a glove box.

On the ITO transparent electrode, a coating composition in which the following compound O and compound P (weight ratio of 2:8) were dissolved in cyclohexanone at 20 wt/v% was spin-coated (4000 rpm) and heat-treated (curing) at 200 ° C. for 30 minutes ) to form a hole injection layer with a thickness of 400 Å. On the hole injection layer, a coating composition in which the following compound Q (Mn: 27,900; Mw: 35,600; measured by GPC using PC Standard using an Agilent 1200 series) was dissolved in toluene at 6 wt/v% was spin-coated ( 4000 rpm) and heat-treated at 200 °C for 30 minutes to form a hole transport layer having a thickness of 200 Å. On the hole transport layer, a coating composition prepared by dissolving Compound 1 and Compound R (2:98 in weight ratio) at 2 wt/v% in cyclohexanone was spin-coated (4000 rpm) and heat-treated at 180° C. for 30 minutes. A light emitting layer was formed to a thickness of 400 Å. After transferring to a vacuum evaporator, the following compound S was vacuum deposited to a thickness of 350 Å on the light emitting layer to form an electron injection and transport layer. A cathode was formed by sequentially depositing LiF to a thickness of 10 Å and aluminum to a thickness of 1000 Å on the electron injection and transport layer.

In the above process, the deposition rate of organic materials was maintained at 0.4 to 0.7 Å / sec, LiF was maintained at 0.3 Å / sec, and aluminum was maintained at 2 Å / sec, and the vacuum degree during deposition was 2 * 10 ^-7 to 5 *10 ^-8 torr was maintained.

Experimental Examples 2 to 36

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

Comparative Experimental Examples 1 to 3

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

When a current was applied to the organic light emitting device prepared in the above Experimental Examples and Comparative Experimental Examples, the driving voltage at a current density of 10 mA / cm ² , the external quantum efficiency (EQE) and the lifespan measurement results It is shown in Table 1 below. At this time, the external quantum efficiency (EQE) was obtained as “(number of photons emitted) / (number of charge carriers injected) * 100”, and T90 is the time required for the luminance to decrease from the initial luminance (500 nit) to 90% means

division light emitting layer
dopant driving voltage
(V@10mA/cm ² ) EQE
(%@10mA/cm ² ) Life (hr)
(T90@500 nits) Experimental Example 1 compound 1 4.68 6.06 245 Experimental Example 2 compound 2 4.63 6.02 243 Experimental Example 3 compound 3 4.67 6.04 247 Experimental Example 4 compound 4 4.64 6.07 242 Experimental Example 5 compound 5 4.60 6.01 247 Experimental Example 6 compound 6 4.63 6.04 230 Experimental Example 7 compound 7 4.59 6.03 240 Experimental Example 8 compound 8 4.67 6.01 245 Experimental Example 9 compound 9 4.62 5.98 239 Experimental Example 10 compound 10 4.62 6.05 242 Experimental Example 11 compound 11 4.61 6.01 245 Experimental Example 12 compound 12 4.60 6.04 239 Experimental Example 13 compound 13 4.59 6.04 235 Experimental Example 14 compound 14 4.58 5.98 240 Experimental Example 15 compound 15 4.62 5.99 241 Experimental Example 16 compound 16 4.63 6.00 240 Experimental Example 17 compound 17 4.67 6.08 239 Experimental Example 18 compound 18 4.61 6.01 238 Experimental Example 19 compound 19 4.64 6.02 242 Experimental Example 20 compound 20 4.63 6.05 242 Experimental Example 21 compound 21 4.60 6.04 241 Experimental Example 22 compound 22 4.58 6.02 245 Experimental Example 23 compound 23 4.59 6.05 242 Experimental Example 24 compound 24 4.67 6.05 246 Experimental Example 25 compound 25 4.63 6.07 240 Experimental Example 26 compound 26 4.60 6.08 230 Experimental Example 27 compound 27 4.62 6.01 242 Experimental Example 28 compound 28 4.62 6.03 242 Experimental Example 29 compound 29 4.67 6.04 245 Experimental Example 30 compound 30 4.62 6.06 240 Experimental Example 31 compound 31 4.60 6.05 241 Experimental Example 32 compound 32 4.63 6.04 246 Experimental Example 33 compound 33 4.68 6.02 242 Experimental Example 34 compound 34 4.63 6.01 235 Experimental Example 35 compound 35 4.60 6.09 249 Experimental Example 36 compound 36 4.62 6.08 242 Comparative Experimental Example 1 compound F 4.69 4.39 105 Comparative Experimental Example 2 compound G 4.68 4.23 99 Comparative Experimental Example 3 compound H 4.62 3.98 83

As shown in Table 1, the organic light emitting device including the compound of the present invention in the light emitting layer exhibited excellent characteristics in terms of efficiency, driving voltage, and lifetime of the organic light emitting device.

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

Claims (10)

A compound represented by Formula 1 below:
[Formula 1]

In Formula 1,
A is each independently a substituted or unsubstituted C _3-10 cycloalkane ring fused with an adjacent ring,
R ₁ to R ₄ are each independently hydrogen, deuterium, or substituted or unsubstituted C _1-60 alkyl, or two adjacent R ₁ to R ₄ are bonded together to form substituted or unsubstituted C _6-60 form an aryl;
R ₅ are each independently hydrogen, deuterium, or substituted or unsubstituted C _1-60 alkyl;
R ₆ are each independently hydrogen, deuterium, or substituted or unsubstituted C _1-60 alkyl;
R' ₁ and R' ₂ are each independently hydrogen, deuterium, or substituted or unsubstituted C _1-60 alkyl;
a, b, c, and d are each independently an integer from 2 to 16;
n is an integer from 1 to 10;
According to claim 1,
A is each independently a substituted or unsubstituted cyclopentane or cyclohexane ring fused with an adjacent ring;
compound.
According to claim 1,
R ₁ to R ₄ are each independently hydrogen, deuterium, or methyl, or two adjacent R ₁ to R ₄ combine with each other to form substituted or unsubstituted benzene;
compound.
According to claim 1,
Formula 1 is represented by any one selected from the group consisting of Formula 1-1 to Formula 1-16
compound:

In Formulas 1-1 to 1-16,
R ₅ , R ₆ , R' ₁ , R' ₂ , and n are as defined in claim 1.
According to claim 1,
R ₅ and R ₆ are each independently hydrogen, deuterium, or methyl;
compound.
According to claim 1,
R' ₁ and R' ₂ are each independently hydrogen, deuterium, methyl, isopropyl, or tertbutyl;
compound.
According to claim 1,
n is an integer from 2 to 5;
compound.
According to claim 1,
The compound represented by Formula 1 is any one selected from the group consisting of the following compounds,
compound:

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 according to any one of claims 1 to 8. , an organic light emitting device.
According to claim 9,
The organic material layer is a light emitting layer,
organic light emitting device.