CN116583528A - Novel compound and organic light emitting device comprising the same - Google Patents
Novel compound and organic light emitting device comprising the same Download PDFInfo
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- CN116583528A CN116583528A CN202280007832.9A CN202280007832A CN116583528A CN 116583528 A CN116583528 A CN 116583528A CN 202280007832 A CN202280007832 A CN 202280007832A CN 116583528 A CN116583528 A CN 116583528A
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Abstract
The present disclosure provides novel compounds and organic light emitting devices comprising the same.
Description
Technical Field
Cross Reference to Related Applications
The present application claims the benefits of korean patent application No. 10-2021-0000315 filed on 1 month 4 of 2021 and korean patent application No. 10-2022-0000238 filed on 1 month 3 of 2022, the disclosures of which are incorporated herein by reference in their entireties.
The present disclosure relates to novel compounds and organic light emitting devices comprising the same.
Background
In general, an organic light emitting phenomenon refers to a phenomenon in which electric energy is converted into light energy by using an organic material. An organic light emitting device using an organic light emitting phenomenon has characteristics such as a wide viewing angle, excellent contrast, a fast response time, excellent brightness, driving voltage, and response speed, and thus many researches have been conducted.
The organic light emitting device generally has a structure including an anode, a cathode, and an organic material layer interposed between the anode and the cathode. The organic material layer generally has a multi-layered structure including different materials to improve efficiency and stability of the organic light emitting device, and for example, the organic material layer may be formed of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like. In the structure of the organic light emitting device, if a voltage is applied between two electrodes, holes are injected from an anode into an organic material layer, and electrons are injected from a cathode into the organic material layer, excitons are formed when the injected holes and electrons meet each other, and light is emitted when the excitons fall back to a ground state again.
There is a continuing need to develop new materials for organic materials used in organic light emitting devices as described above.
Meanwhile, recently, in order to reduce the process cost, organic light emitting devices using a solution method, particularly an inkjet method, instead of a conventional deposition method have been developed. In the initial stage of development, attempts have been made to develop an organic light emitting device by coating all organic light emitting device layers through a solution method, but the current technology has limitations. Therefore, only the HIL, HTL, and EML are treated by the solution method, and a hybrid method using a conventional deposition method is being studied as a subsequent method.
Accordingly, the present disclosure provides new materials for organic light emitting devices that can be used for organic light emitting devices and at the same time can be used for solution processes.
[ Prior Art literature ]
[ patent literature ]
(patent document 1) Korean unexamined patent publication No. 10-2000-0051826
Disclosure of Invention
Technical problem
It is an object of the present disclosure to provide novel compounds and organic light emitting devices comprising the same.
Technical proposal
According to one aspect of the present disclosure, there is provided a compound represented by the following chemical formula 1:
[ chemical formula 1]
In the chemical formula 1, the chemical formula is shown in the drawing,
a1 to A5 are each independently C 6-60 An aromatic ring; or C comprising at least one of N, O and S 2-60 A heteroaromatic ring which contains at least one aromatic ring,
Ar 1 and Ar is a group 2 Each independently is a substituted or unsubstituted C 6-60 Aromatic compoundsA ring; or substituted or unsubstituted C comprising any one or more of N, O and S 2-60 Heteroaromatic ring, and
at least one of R is benzofuranyl, the remainder each independently being hydrogen; deuterium; halogen; a nitrile group; a nitro group; an amino group; substituted or unsubstituted C 1-60 An alkyl group; substituted or unsubstituted C 3-60 Cycloalkyl; substituted or unsubstituted C 2-60 Alkenyl groups; or C which is substituted or unsubstituted 6-60 Aryl, or two adjacent R's are linked to each other to form a substituted or unsubstituted C 3-6 An alkylene group.
According to another aspect of the present disclosure, there is provided an organic light emitting device including: a first electrode; a second electrode disposed opposite to the first electrode; and one or more organic material layers disposed between the first electrode and the second electrode, wherein one or more of the organic material layers comprises a compound represented by chemical formula 1.
Advantageous effects
The above-described compound represented by chemical formula 1 may be used as a material of an organic material layer for an organic light emitting device, may be used in a solution method, and may improve efficiency, achieve a low driving voltage, and/or improve lifetime characteristics in the organic light emitting device.
Drawings
Fig. 1 shows an example of an organic light emitting device including a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4.
Fig. 2 shows an example of an organic light emitting device including 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.
Detailed Description
Hereinafter, embodiments of the present disclosure will be described in more detail to facilitate understanding of the present application.
(definition of terms)
As used herein, a symbolMeaning a bond to an additional substituent group.
As used herein, the term "substituted or unsubstituted" means unsubstituted or substituted with one or more substituents selected from the group consisting of: deuterium; a halogen group; cyano group; a nitro group; a hydroxyl group; a carbonyl group; an ester group; an imide group; an amino group; a phosphine oxide group; an alkoxy group; an aryloxy group; alkylthio; arylthio; an alkylsulfonyl group; arylsulfonyl; a silyl group; a boron base; an alkyl group; cycloalkyl; alkenyl groups; an aryl group; an aralkyl group; aralkenyl; alkylaryl groups; an alkylamino group; an aralkylamine group; heteroaryl amine groups; an arylamine group; aryl phosphino; and heteroaryl groups comprising at least one of N, O and S atoms, or substituted with substituents that are unsubstituted or linked with two or more of the substituents exemplified above. For example, a "substituent in which two or more substituents are linked" may be a biphenyl group. That is, biphenyl may be aryl, or it may also be interpreted as a substituent to which two phenyl groups are linked.
In the present disclosure, the carbon number of the carbonyl group is not particularly limited, but is preferably 1 to 40. Specifically, the carbonyl group may be a substituent having the following structural formula, but is not limited thereto.
In the present disclosure, the ester group may have a structure in which oxygen of the ester group may be substituted with a linear, branched, or cyclic alkyl group having 1 to 25 carbon atoms or an aryl group having 6 to 25 carbon atoms. Specifically, the ester group may be a substituent having the following structural formula, but is not limited thereto.
In the present disclosure, the carbon number of the imide group is not particularly limited, but is preferably 1 to 25.
Specifically, the imide group may be a substituent having the following structural formula, but is not limited thereto.
In the present disclosure, the silyl group specifically includes, but is not limited to, trimethylsilyl, triethylsilyl, t-butyldimethylsilyl, vinyldimethylsilyl, propyldimethylsilyl, triphenylsilyl, diphenylsilyl, phenylsilyl, and the like.
In the present disclosure, the boron group specifically includes trimethylboron group, triethylboron group, t-butyldimethylboroyl group, triphenylboron group, and phenylboron group, but is not limited thereto.
In the present disclosure, examples of halogen groups include fluorine, chlorine, bromine, or iodine.
In the present disclosure, the alkyl group may be linear or branched, and the carbon number thereof is not particularly limited, but is preferably 1 to 40. According to one embodiment, the alkyl group has a carbon number of 1 to 20. According to another embodiment, the alkyl group has a carbon number of 1 to 10. According to another embodiment, the alkyl group has a carbon number of 1 to 6. Specific examples of the alkyl group include, but are not limited to, 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-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2-dimethylheptyl, 1-ethyl-propyl, 1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl and the like.
In the present disclosure, the alkenyl group may be linear or branched, and the carbon number thereof is not particularly limited, but is preferably 2 to 40. According to one embodiment, the alkenyl group has a carbon number of 2 to 20. According to another embodiment, the alkenyl group has a carbon number of 2 to 10. According to yet another embodiment, the alkenyl group has a carbon number of 2 to 6. Specific examples thereof include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-methyl-1-butenyl, 1, 3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-diphenylvinyl-1-yl, 2-phenyl-2- (naphthalen-1-yl) vinyl-1-yl, 2-bis (diphenyl-1-yl) vinyl-1-yl, stilbene, styryl and the like, but are not limited thereto.
In the present disclosure, the cycloalkyl group is not particularly limited, but the carbon number thereof is preferably 3 to 60. According to one embodiment, the cycloalkyl group has a carbon number of 3 to 30. According to another embodiment, the cycloalkyl group has a carbon number of 3 to 20. According to yet another embodiment, the cycloalkyl group has a carbon number of 3 to 6. Specific examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2, 3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2, 3-dimethylcyclohexyl, 3,4, 5-trimethylcyclohexyl, 4-t-butylcyclohexyl, cycloheptyl, cyclooctyl and the like, but are not limited thereto.
In the present disclosure, the aryl group is not particularly limited, but the carbon number thereof is preferably 6 to 60, and it may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the aryl group has a carbon number of 6 to 30. According to one embodiment, the aryl group has a carbon number of 6 to 20. The aryl group may be phenyl, biphenyl, terphenyl, etc. as a monocyclic aryl group, but is not limited thereto. Polycyclic aryl groups include naphthyl, anthryl, phenanthryl, pyrenyl, perylenyl,A radical, a fluorenyl radical, etc., but is not limited thereto.
In the present disclosure, the fluorenyl group may be substituted, and two substituents may be linked to each other to form a spiro structure. In the case where the fluorenyl group is substituted, it may be formedEtc. HoweverThe structure is not limited thereto.
In the present disclosure, the heteroaryl group is a heteroaryl group including at least one of O, N, si and S as a heteroatom, and the carbon number thereof is not particularly limited, but is preferably 2 to 60. Examples of heteroaryl groups include xanthenyl, thioxanthenyl, thienyl, furyl, pyrrolyl, imidazolyl, thiazolyl,Azolyl, (-) -and (II) radicals>Diazolyl, triazolyl, pyridyl, bipyridyl, pyrimidinyl, triazinyl, acridinyl, pyridazinyl, pyrazinyl, quinolinyl, quinazolinyl, quinoxalinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, pyrazinopyrazinyl, isoquinolinyl, indolyl, carbazolyl, benzo->Oxazolyl, benzimidazolyl, benzothiazolyl, benzocarbazolyl, benzothienyl, dibenzothiophenyl, benzofuranyl, phenanthrolinyl, and i ∈ ->Oxazolyl, thiadiazolyl, phenothiazinyl, dibenzofuranyl, and the like, but are not limited thereto.
In the present disclosure, the aryl groups in the aralkyl group, the aralkenyl group, the alkylaryl group, the arylamine group, and the arylsilyl group are the same as the examples of the above aryl groups. In the present disclosure, the alkyl groups in the aralkyl group, the alkylaryl group, and the alkylamino group are the same as the examples of the alkyl groups described above. In the present disclosure, heteroaryl groups in heteroaryl amines may be suitable for use in the description of heteroaryl groups described above. In the present disclosure, alkenyl groups in aralkenyl groups are the same as the examples of alkenyl groups described above. In the present disclosure, the above description of aryl groups may be applied, except that arylene groups are divalent groups. In the present disclosure, the above description of heteroaryl groups may be applied, except that the heteroarylene group is a divalent group. In the present disclosure, the above description of aryl or cycloalkyl groups may be applied, except that the hydrocarbon ring is not a monovalent group but is formed by combining two substituents. In the present disclosure, the above description of heteroaryl groups may be applied, except that the heterocycle is not a monovalent group but is formed by combining two substituents.
(Compound)
The present disclosure provides a compound represented by chemical formula 1.
The compound represented by chemical formula 1 introduces an amine substituent in the molecular structure to reduce an electron vibration peak of the compound, thereby reducing the full width at half maximum of an emission spectrum and improving the color purity of the organic light emitting device.
In chemical formula 1, preferably, A2 and A3 are the same, and A4 and A5 are the same.
Preferably, A1 to A5 are each independently C 6-10 An aromatic ring; or C comprising any one or more of N, O and S 2-12 Heteroaromatic rings. More preferably, A1 to A5 are each independently benzene, naphthalene, benzofuran, dibenzofuran, benzothiophene, dibenzothiophene, 1-phenylindole, or 9-phenylindole. More preferably, all of A1 to A5 are benzene.
Preferably, chemical formula 1 is represented by the following chemical formula 1-1:
[ chemical formula 1-1]
In the chemical formula 1-1, a radical of formula,
Ar 1 、Ar 2 and R is as defined above.
Preferably Ar 1 And Ar is a group 2 Each independently is benzene, biphenyl, naphthalene, dimethylfluorene, diphenylfluorene, dimethylbenzofluorene or diphenylbenzofluorene. Here, dimethylbenzofluorene and diphenylbenzofluorene preferably have the following structures, respectively.
Preferably, at least one of R is benzofuranyl, the remainder each independently being hydrogen; deuterium; or C which is substituted or unsubstituted 1-10 An alkyl group; or two adjacent R's are linked to each other to form
Preferably, at least one of R is benzofuranyl, the remainder each independently being hydrogen; deuterium; a methyl group; an ethyl group; a propyl group; an isopropyl group; a butyl group; an isobutyl group; or tert-butyl; or two adjacent R's are linked to each other to form
Preferably, one to three of R are benzofuranyl.
Preferably, the benzofuranyl group is benzofuran-2-yl
Preferably, chemical formula 1 is represented by any one of the following chemical formulas 2 to 4:
[ chemical formula 2]
[ chemical formula 3]
[ chemical formula 4]
In the chemical formulas 2 to 4,
Ar 1 and Ar is a group 2 As defined above, and
at least one of R is benzofuranyl, the remainder each independently being hydrogen; deuterium; halogen; a nitrile group; a nitro group; an amino group; substituted or unsubstituted C 1-60 An alkyl group; substituted or unsubstituted C 3-60 Cycloalkyl; substituted or unsubstituted C 2-60 Alkenyl groups; or C which is substituted or unsubstituted 6-60 Aryl groups.
Representative examples of the compound represented by chemical formula 1 are as follows:
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meanwhile, the present disclosure provides a method for preparing a compound represented by chemical formula 1 (wherein A2 and A3 are the same and A4 and A5 are the same) as shown in, for example, reaction scheme 1 below, and other remaining compounds may be prepared by applying the following reaction scheme.
Reaction scheme 1
In reaction scheme 1, the definition of the remaining substituents other than X is the same as defined above, and X is halogen, preferably bromine or chlorine.
Step 1 and step 2 are amine substitution reactions, which are preferably carried out in the presence of a palladium catalyst and a base, and the reactive groups for the amine substitution reactions may be modified as known in the art. Step 3 is with BI 3 Preferably in the presence of a base. The above preparation method may be further embodied in the preparation examples described below.
(coating composition)
On the other hand, the compound according to the present disclosure may form an organic material layer, particularly a light emitting layer, of an organic light emitting device by a solution method. In particular, the compound may be used as a dopant material of the light emitting layer. For this purpose, the present disclosure provides a coating composition comprising the above-described compound according to the present disclosure and a solvent.
The solvent is not particularly limited as long as it is a solvent capable of dissolving or dispersing the compound according to the present disclosure. Examples of the solvent may include chlorine-based solvents such as chloroform, methylene chloride, 1, 2-dichloroethane, 1, 2-trichloroethane, chlorobenzene and o-dichlorobenzene; ether-based solvents, e.g. tetrahydrofuran and diAn alkane; solvents based on aromatic hydrocarbons, 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-based solvents such as acetone, methyl ethyl ketone, and cyclohexanone; ester-based solvents such as ethyl acetate, butyl acetate, and ethyl cellosolve acetate; polyhydric alcohols such as ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, dimethoxyethane, propylene glycol, diethoxymethane, triethylene glycol monoethyl ether, glycerol and 1, 2-hexanediol, and derivatives thereof; alcohol-based solvents such as methanol, ethanol, propanol, isopropanol, and cyclohexanol; sulfoxide-based solvents, e.g. dimethyl sulfoxideThe method comprises the steps of carrying out a first treatment on the surface of the Amide-based solvents such as N-methyl-2-pyrrolidone and N, N-dimethylformamide; benzoate-based solvents, such as butyl benzoate and methyl-2-methoxybenzoate; tetralin; 3-phenoxy-toluene; etc. Further, the above solvents may be used alone or in combination of two or more solvents. Preferably, toluene may be used as a solvent.
In addition, the coating composition may further contain a compound used as a host material, and the compound used for the host material will be described later. Further, the coating composition may contain a compound used as a dopant material, and the compound used for the dopant material will be described later.
Further, the viscosity of the coating composition is preferably 1cP to 10cP, and coating is easily performed within the above range. Furthermore, the concentration of the compound according to the present disclosure in the coating composition is preferably 0.1 to 20 wt/vol%.
In another embodiment of the present disclosure, a method of forming a light emitting layer using the above-described coating composition is provided. Specifically, the method comprises the steps of: coating the light emitting layer according to the present disclosure described above on the anode by a solution method; and heat treating the applied coating composition.
The solution method uses the above-described coating composition according to the present disclosure, and refers to spin coating, dip coating, knife coating, ink jet printing, screen printing, spray method, roll coating, and the like, but is not limited thereto.
The heat treatment temperature in the heat treatment step is preferably 150 ℃ to 230 ℃. Further, the heat treatment time may be 1 minute to 3 hours, more preferably 10 minutes to 1 hour. Further, the heat treatment is preferably performed in an inert gas atmosphere such as argon and nitrogen.
(organic light-emitting device)
In another embodiment of the present disclosure, an organic light emitting device including the compound represented by chemical formula 1 is provided. In one example, the present disclosure provides an organic light emitting device comprising: a first electrode; a second electrode disposed opposite to the first electrode; and one or more organic material layers disposed between the first electrode and the second electrode, wherein one or more of the organic material layers comprises a compound represented by chemical formula 1.
The organic material layer of the organic light emitting device of the present disclosure may have a single layer structure, or it 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 disclosure may have a structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like as an organic material layer. However, the structure of the organic light emitting device is not limited thereto, and it may include a smaller number of organic layers.
Further, the organic material layer may include a light emitting layer, wherein the light emitting layer may include a compound represented by chemical formula 1. In particular, compounds according to the present disclosure may be used as dopants for light emitting layers.
Further, the organic light emitting device according to the present disclosure 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. Further, the organic light emitting device according to the present disclosure may be an inverted organic light emitting device 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 one embodiment of the present disclosure is shown in fig. 1 and 2.
Fig. 1 shows an example of an organic light emitting device including a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4. In such a structure, the compound represented by chemical formula 1 may be included in the light emitting layer.
Fig. 2 shows an example of an organic light emitting device including 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. In such a 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 disclosure may be manufactured by materials and methods known in the art, except that at least one of the organic material layers includes a compound represented by chemical formula 1. In addition, 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, an organic light emitting device according to the present disclosure may be manufactured by sequentially stacking an anode, an organic material layer, and a cathode on a substrate. In this case, the organic light emitting device may be manufactured by: a metal, a metal oxide having conductivity, or an alloy thereof is deposited on a substrate using a PVD (physical vapor deposition) method such as a sputtering method or an electron beam evaporation method to form an anode, an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer is formed on the anode, and then a material that can function as a cathode is deposited on the organic material layer.
In addition to such a method, the organic light emitting device may be manufactured by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate (international publication 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 alternatively, the first electrode is a cathode and the second electrode is an anode.
As the anode material, a material having a large work function is generally preferably used so that holes can be smoothly injected into the organic material 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 Tin Oxide (ITO), and Indium Zinc Oxide (IZO); combinations of metals and oxides, e.g. ZnO, al or SnO 2 Sb; conductive compounds, e.g. poly (3-methylthiophene), poly [3,4- (ethylene-1, 2-dioxy) thiophene](PEDOT), polypyrrole, and polyaniline; etc., but is not limited thereto.
As the cathode material, it is generally preferable to use a material having a small work function so that electrons can be easily injected into the organic material layer. Specific examples of the cathode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or a combination thereofGold; multilayer structural materials, e.g. LiF/Al or LiO 2 Al; etc., but is not limited thereto.
The hole injection layer is a layer for injecting holes from the electrode, and the hole injection material is preferably a compound of: it has a capability of transporting holes, and thus has a hole injection effect in the anode and a hole injection effect excellent for the light emitting layer or the light emitting material, prevents excitons generated in the light emitting layer from moving to the electron injection layer or the electron injection material, and also has an excellent capability of forming a thin film. Preferably, the HOMO (highest occupied molecular orbital) of the hole injection material is between the work function of the anode material and the HOMO of the surrounding organic material layer. Specific examples of the hole injection material include metalloporphyrin, oligothiophene, arylamine-based organic material, hexanitrile hexaazabenzophenanthrene-based organic material, quinacridone-based organic material, perylene-based organic material, anthraquinone, polyaniline, and polythiophene-based conductive polymer, and the like, 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 suitably a material having a large hole mobility, which can receive holes from the anode or the hole injection layer and transport the holes to the light emitting layer. Specific examples thereof include an arylamine-based organic material, a conductive compound, a block copolymer in which a conjugated moiety and a non-conjugated moiety are simultaneously present, and the like, but are not limited thereto.
The light emitting layer may include a host material and a dopant material. The host material may be a fused aromatic ring derivative, a heterocyclic ring-containing compound, or the like. Specific examples of the condensed aromatic ring derivative include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, and the like. Examples of the heterocycle-containing compound include carbazole derivatives, dibenzofuran derivatives, ladder-type furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.
Examples of dopant materials include aromatic amine derivatives, styrene amine compounds, boron complexes, fluoranthene compounds, metal complexes, and the like. In particular, the aromatic amine derivative is substituted or unsubstitutedAnd examples thereof include pyrene, anthracene having an arylamino group,Bisindenopyrene (periflanthene), and the like. The styrylamine compound is a compound in which at least one arylvinyl group is substituted in a substituted or unsubstituted arylamine, wherein one or two or more substituents selected from the group consisting of aryl, silyl, alkyl, cycloalkyl, and arylamino groups are substituted or unsubstituted. Specific examples thereof include, but are not limited to, styrylamine, styrylenediamine, styrylenetriamine, styrenetetramine, and the like. Further, the metal complex includes iridium complex, platinum complex, and the like, but is not limited thereto.
The electron injection and transport layer is a layer that functions as both an electron transport layer and an electron injection layer, which injects electrons from the electrode and transports the received electrons to the light emitting layer and is formed on the light emitting layer or the electron modulation layer. The electron injecting and transporting material is suitably such a material: electrons from the cathode can be well received and transported to the light emitting layer, and have a large electron mobility. Specific examples of the electron injecting and transporting material include: al complexes of 8-hydroxyquinoline; comprising Alq 3 Is a complex of (a) and (b); an organic radical compound; hydroxyflavone-metal complexes, triazine derivatives; etc., but is not limited thereto. Alternatively, liF, naF, naCl, csF, li can be used 2 O, baO fluorenone, anthraquinone dimethane, diphenoquinone, thiopyran dioxide,Azole,/->Diazoles, triazoles, imidazoles, perylenetetracarboxylic acids, fluorenylenemethanes, anthrones, and the like, and derivatives thereof, metal complex compounds, nitrogen-containing 5-membered ring derivatives, and the like, but are not limited thereto.
Examples of the metal complex compound include, but are not limited to, lithium 8-hydroxyquinoline, zinc bis (8-hydroxyquinoline), copper bis (8-hydroxyquinoline), manganese bis (8-hydroxyquinoline), aluminum tris (2-methyl-8-hydroxyquinoline), gallium tris (8-hydroxyquinoline), beryllium bis (10-hydroxybenzo [ h ] quinoline), zinc bis (2-methyl-8-quinoline) chlorogallium, gallium bis (2-methyl-8-quinoline) (o-cresol), aluminum bis (2-methyl-8-quinoline) (1-naphthol), gallium bis (2-methyl-8-quinoline) (2-naphthol), and the like.
The organic light emitting device according to the present disclosure may be of a front-side emission type, a rear-side emission type, or a double-side emission type, based on the materials used.
Further, the compound according to the present disclosure may be contained in an organic solar cell or an organic transistor in addition to an organic light emitting device.
The preparation of the compound represented by chemical formula 1 and the organic light emitting device including the same will be specifically described in the following examples. However, the following examples are provided for illustrative purposes only and are not intended to limit the scope of the present disclosure.
Examples (example)
Example 1: preparation of compound BD8
Compound 1-a (1.1 eq), naOt-Bu (2.0 eq) and compound 1-b (1.0 eq) were placed in a round bottom flask and dissolved in anhydrous toluene (0.05M). Pd (t-Bu) was added dropwise thereto at a bath temperature of 120 ℃ 3 P) 2 (5 mol%) and the mixture was stirred overnight. After the reaction, the reaction mixture was thoroughly cooled at room temperature, with CH 2 Cl 2 Sufficiently diluted and then used with CH 2 Cl 2 Washing with brine. The organic layer was separated with MgSO 4 The water was removed and passed through a Celite-Florisil-Silica pad. The resulting solution was concentrated under reduced pressure, followed by purification by column chromatography to prepare compound 1-c (yield: 80%).
Compounds 1-c (1 eq), naOt-Bu (2.0 eq) and 1-d (1.0.)Amount) was placed in a round bottom flask and dissolved in anhydrous toluene (0.05M). Pd (t-Bu) was added dropwise thereto at a bath temperature of 120 ℃ 3 P) 2 (5 mol%) and the mixture was stirred overnight. After the reaction, the reaction mixture was thoroughly cooled at room temperature, with CH 2 Cl 2 Sufficiently diluted and then used with CH 2 Cl 2 Washing with brine. The organic layer was separated with MgSO 4 The water was removed and passed through a celite-florisil-silica pad. The resulting solution was concentrated under reduced pressure, followed by purification by column chromatography to prepare compound 1-e (yield: 82%).
Compound 1-e (equivalent), naOt-Bu (2.0 equivalent) and compound 1-f (1.0 equivalent) were placed in a round bottom flask and dissolved in anhydrous toluene (0.05M). Pd (t-Bu) was added dropwise thereto at a bath temperature of 120 ℃ 3 P) 2 (5 mol%) and the mixture was stirred overnight. After the reaction, the reaction mixture was thoroughly cooled at room temperature, with CH 2 Cl 2 Sufficiently diluted and then used with CH 2 Cl 2 Washing with brine. The organic layer was separated with MgSO 4 The water was removed and passed through a celite-florisil-silica pad. The resulting solution was concentrated under reduced pressure, followed by purification by column chromatography to prepare compound 1-g (yield: 72%).
Compound 1-g (1.0 eq) was placed in a round bottom flask and dissolved in anhydrous toluene (0.03M). Slowly dropwise adding BI into the reaction solution 3 (2.0 eq.) and the mixture was stirred at 80 ℃ bath temperature overnight. After the reaction, the reaction mixture was thoroughly cooled at room temperature and taken up with CH 2 Cl 2 And (5) fully diluting. Sequential drops of EtNi-Pr into the reaction mixture 2 (15.0 eq.) and saturated Na 2 S 2 O 3 (aqueous solution) and using CH 2 Cl 2 /H 2 And (3) washing. The organic layer was separated with MgSO 4 The water was removed and passed through a celite-florisil-silica pad. The resulting solution was concentrated under reduced pressure, followed by purification by column chromatography to prepare compound BD8 (yield: 60%).
m/z[M+H] + 1154.5
Example 2: preparation of compound BD12
Compound 2-a (1 eq), naOt-Bu (4.0 eq) and compound 2-b (2.0 eq) were placed in a round bottom flask and dissolved in anhydrous toluene (0.05M). Pd (t-Bu) was added dropwise thereto at a bath temperature of 120 ℃ 3 P) 2 (10 mol%) and the mixture was stirred overnight. After the reaction, the reaction mixture was thoroughly cooled at room temperature, with CH 2 Cl 2 Sufficiently diluted and then used with CH 2 Cl 2 Washing with brine. The organic layer was separated with MgSO 4 The water was removed and passed through a celite-florisil-silica pad. The resulting solution was concentrated under reduced pressure, followed by purification by column chromatography to prepare compound 2-e (yield: 70%).
Subsequently, compound BD12 was prepared in the same manner as in the preparation method of compound BD8, except that compound 2-c was used instead of compound 1-e, and compound 2-d was used instead of compound 1-f.
m/z[M+H] + 1094.6
Example 3: preparation of compound BD29
/>
Compound BD29 was prepared in the same manner as in the preparation method of compound BD12, except that compound 3-d was used instead of compound 2-d.
m/z[M+H] + 1094.6
Example 4: preparation of Compound BD37
Compound BD37 was produced in the same manner as in the production method of compound BD12, except that compound 4-b was used instead of compound 2-b, and compound 4-d was used instead of compound 2-d.
m/z[M+H] + 1142.6
Example 5: preparation of compound BD44
Compound BD44 was produced in the same manner as in the production method of compound BD8, except that compound 5-b was used instead of compound 1-b, and compound 5-d was used instead of compound 1-d.
m/z[M+H] + 1102.1
Example 6: preparation of compound BD45
Compound BD37 was produced in the same manner as in the production method of compound BD12, except that compound 6-b was used instead of compound 2-b, and compound 6-d was used instead of compound 2-d.
m/z[M+H] + 992.4
Example 7: preparation of compound BD75
Compound BD75 was produced in the same manner as in the production method of compound BD12, except that compound 7-b was used instead of compound 2-b, and compound 7-d was used instead of compound 2-d.
m/z[M+H] + 932.4
Example 8: preparation of Compound BD76
Compound BD76 was prepared in the same manner as in the preparation method of compound BD8, except that compound 8-d, compound 1-d, and compound 1-b, were used instead of compound 1-f.
m/z[M+H] + 1048.5
Example 9: preparation of compound BD30
Compound BD30 was prepared in the same manner as in the preparation method of compound BD12, except that compound 9-d was used instead of compound 2-d.
m/z[M+H] + 1144.6
Example 10: preparation of compound BD82
Compound BD82 was produced in the same manner as in the production method of compound BD12, except that compound 10-d was used instead of compound 2-d.
m/z[M+H] + 1044.6
Comparative example
Comparative example 1: preparation of Compound F
Compound F-1 (1.0 eq), naOt-Bu (4.0 eq) and compound F-2 (2.05 eq) were placed in a round bottom flask and dissolved in anhydrous toluene (0.1M). Pd (t-Bu) was added dropwise thereto at a bath temperature of 120 ℃ 3 P) 2 (5 mol%) and the mixture was stirred for 3 days. After the reaction, the reaction mixture was thoroughly cooled at room temperature, with CH 2 Cl 2 Sufficiently diluted and then used with CH 2 Cl 2 Washing with brine. The organic layer was separated with MgSO 4 Remove water and pass through celite-FrenchSilica-silica pad. The resulting solution was concentrated under reduced pressure, followed by purification by column chromatography to prepare compound F-3 (yield: 75%).
Compound F-3 (1.0 eq) was placed in a round bottom flask and dissolved in anhydrous toluene (0.03M). To which BI is slowly added dropwise 3 (2.0 eq.) and the mixture was stirred at 80 ℃ bath temperature overnight. After the reaction, the reaction mixture was thoroughly cooled at room temperature, with CH 2 Cl 2 And (5) fully diluting. Sequential drops of EtNi-Pr into the reaction mixture 2 (15.0 eq.) and saturated Na 2 S 2 O 3 (aqueous solution) and using CH 2 Cl 2 /H 2 And (3) washing. The organic layer was separated with MgSO 4 The water was removed and passed through a celite-florisil-silica pad. The resultant solution was concentrated under reduced pressure, followed by purification by column chromatography to prepare compound F (yield: 87%).
m/z[M+H] + 659.6
Comparative example 2: preparation of Compound G
Compound G was prepared in the same manner as in comparative example 1 except that compound G-1 was used instead of compound F-2.
m/z[M+H] + 659.5
Comparative example 3: preparation of Compound H
Compound H-1 (1.0 eq), naOt-Bu (4.0 eq) and compound H-2 (1.05 eq) were placed in a round bottom flask and dissolved in anhydrous toluene (0.1M). Pd (t-Bu) was added dropwise thereto at a bath temperature of 120 ℃ 3 P) 2 (5 mol%) and the mixture was stirred overnight. After the reaction, the reaction mixture was thoroughly cooled at room temperature, with CH 2 Cl 2 The mixture is fully diluted and the mixture is fully diluted,then using CH 2 Cl 2 Washing with brine. The organic layer was separated with MgSO 4 The water was removed and passed through a celite-florisil-silica pad. The resulting solution was concentrated under reduced pressure, followed by purification by column chromatography to prepare compound H-3 (yield: 79%).
Compound H-3 (1.0 eq) was placed in a round bottom flask and dissolved in anhydrous toluene (0.03M). To which BI is slowly added dropwise 3 (2.0 eq.) and the mixture was stirred at 80 ℃ bath temperature overnight. After the reaction, the reaction mixture was thoroughly cooled at room temperature, with CH 2 Cl 2 And (5) fully diluting. Sequential drops of EtNi-Pr into the reaction mixture 2 (15.0 eq.) and saturated Na 2 S 2 O 3 (aqueous solution) and using CH 2 Cl 2 /H 2 And (3) washing. The organic layer was separated with MgSO 4 The water was removed and passed through a celite-florisil-silica pad. The resultant solution was concentrated under reduced pressure, followed by purification by column chromatography to prepare compound H (yield: 73%).
m/z[M+H] + 725.5
Experimental example
Experimental example 1
Coated with a coating having a thickness ofThe glass substrate as a thin film was put into distilled water in which a cleaning agent was dissolved, and subjected to ultrasonic cleaning. At this time, a product manufactured by fischer co was used as a detergent, and as distilled water, distilled water filtered twice using a filter manufactured by Millipore co was used. After washing the ITO for 30 minutes, the ultrasonic washing was repeated twice using distilled water for 10 minutes. After the washing with distilled water was completed, the substrate was ultrasonically washed with isopropanol, acetone and methanol solvents, dried, and then the substrate was washed for 5 minutes, and then transferred to a glove box.
Spin coating (4000 rpm) on ITO transparent electrode coating in which the following compound O and the following compound P (weight ratio of 2:8) were dissolved in cyclohexanone at 20% by weight/volumeCoating the composition and heat treating (curing) at 200 ℃ for 30 minutes to form a coating having a thicknessIs provided. Spin-coating (4000 rpm) a coating composition in which the following polymer Q (Mn: 27,900; mw:35,600; measured by GPC (Agilent 1200 series) using PC standards) was dissolved in toluene at 6 wt/vol%, and heat-treating at 200℃for 30 minutes to form a coating composition having a thickness ±>Is provided. Coating composition in which previously prepared compound BD8 and following compound R (weight ratio 2:98) were dissolved in cyclohexanone at 2 wt/vol% was spin-coated (4000 rpm) on the hole transport layer, and heat-treated at 180 ℃ for 30 minutes to form a thickness ofIs provided. After transfer to the vacuum evaporator, the following compound S was vacuum deposited on the light-emitting layer to form a film having a thickness +.>Electron injection and transport layers of (a) are provided. Deposition of LiF on electron injection and transport layer sequentially>And aluminumTo form a cathode.
In the above process, the vapor deposition rate of the organic material is maintained atSecond to->Per second, the deposition rate of LiF is kept +.>Per second, the deposition rate of aluminum is kept +.>Per second, and maintain the vacuum level during deposition at 2 x 10 -7 To 5X 10 -8 And (5) a bracket.
Experimental examples 2 to 10
An organic light-emitting device was manufactured in the same manner as in experimental example 1, except that the compound shown in table 1 below was used as a dopant of the light-emitting layer instead of the compound BD 8.
Comparative 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 below was used as a dopant of the light-emitting layer instead of the compound BD 8.
By applying 10mA/cm to the organic light emitting devices manufactured in the experimental examples and the comparative experimental examples 2 The driving voltage, external Quantum Efficiency (EQE), and lifetime were measured, and the results are shown in table 1 below. At this time, the External Quantum Efficiency (EQE) is calculated as "(number of emitted photons)/(number of injected charge carriers) ×100", and the lifetime (T90) means the time required for the luminance to decrease to 90% of the initial luminance (500 nit). Further, full width at half maximum (FWHM) of the compound used as a dopant of the light emitting layer was measured and is shown together in table 1 below.
TABLE 1
As shown in table 1 above, the organic light emitting device including the compound of the present disclosure as a dopant of the light emitting layer exhibits excellent characteristics in terms of efficiency, driving voltage, and lifetime.
[ reference numerals ]
1: substrate 2: anode
3: light emitting layer 4: cathode electrode
5: hole injection layer 6: hole transport layer
7: light emitting layer 8: electron injection and transport layers
Claims (12)
1. A compound represented by the following chemical formula 1:
[ chemical formula 1]
In the chemical formula 1, the chemical formula is shown in the drawing,
a1 to A5 are each independently C 6-60 An aromatic ring; or C comprising at least one of N, O and S 2-60 A heteroaromatic ring which contains at least one aromatic ring,
Ar 1 and Ar is a group 2 Each independently is a substituted or unsubstituted C 6-60 An aromatic ring; or substituted or unsubstituted C comprising any one or more of N, O and S 2-60 Heteroaromatic ring, and
at least one of R is benzofuranyl and the remainder are each independently hydrogen; deuterium; halogen; a nitrile group; a nitro group; an amino group; substituted or unsubstituted C 1-60 An alkyl group; substituted or unsubstituted C 3-60 Cycloalkyl; substituted or unsubstituted C 2-60 Alkenyl groups; or C which is substituted or unsubstituted 6-60 Aryl, or two adjacent R's are linked to each other to form a substituted or unsubstituted C 3-6 An alkylene group.
2. A compound according to claim 1, wherein:
a2 and A3 are the same, and
a4 and A5 are the same.
3. A compound according to claim 1, wherein:
the chemical formula 1 is represented by the following chemical formula 1-1:
[ chemical formula 1-1]
Wherein in the chemical formula 1-1,
Ar 1 、Ar 2 and R is as defined in claim 1.
4. A compound according to claim 1, wherein:
Ar 1 and Ar is a group 2 Each independently is phenyl, biphenyl, naphthyl, dimethylfluorenyl, diphenylfluorenyl, dimethylbenzofluorenyl, or diphenylbenzofluorenyl.
5. A compound according to claim 1, wherein:
at least one of R is benzofuranyl and the remainder are each independently hydrogen; deuterium; or C which is substituted or unsubstituted 1-10 An alkyl group; or two adjacent R's are linked to each other to form
6. A compound according to claim 1, wherein:
at least one of R is benzofuranyl and the remainder are each independently hydrogen; deuterium; a methyl group; an ethyl group; a propyl group; an isopropyl group; a butyl group; an isobutyl group; or tert-butyl; or two adjacent R's are linked to each other to form
7. A compound according to claim 1, wherein:
one to three of R are benzofuranyl.
8. A compound according to claim 1, wherein:
the benzofuranyl group is benzofuranyl-2-yl.
9. A compound according to claim 1, wherein:
the chemical formula 1 is represented by any one of the following chemical formulas 2 to 4:
[ chemical formula 2]
[ chemical formula 3]
[ chemical formula 4]
Wherein in the chemical formulas 2 to 4,
Ar 1 and Ar is a group 2 As defined in claim 1, and
at least one of R is benzofuranyl, the remainder each independently being hydrogen; deuterium; halogen; a nitrile group; a nitro group; an amino group; substituted or unsubstituted C 1-60 An alkyl group; substituted or unsubstituted C 3-60 Cycloalkyl; substituted or unsubstituted C 2-60 Alkenyl groups; or C which is substituted or unsubstituted 6-60 Aryl groups.
10. A compound according to claim 1, wherein:
the compound represented by chemical formula 1 is any one selected from the following:
11. an organic light emitting device comprising: a first electrode; a second electrode disposed opposite to the first electrode; and one or more layers of organic material disposed between the first electrode and the second electrode, wherein one or more of the layers of organic material comprises a compound as set forth in any one of claims 1 to 10.
12. The organic light-emitting device of claim 11, wherein:
the organic material layer including the compound is a light emitting layer.
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| KR10-2021-0000315 | 2021-01-04 | ||
| KR1020220000238A KR20220098687A (en) | 2021-01-04 | 2022-01-03 | Novel compound and organic light emitting device comprising the same |
| KR10-2022-0000238 | 2022-01-03 | ||
| PCT/KR2022/000036 WO2022146123A1 (en) | 2021-01-04 | 2022-01-04 | Novel compound and organic light-emitting device comprising same |
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| CN116583528A true CN116583528A (en) | 2023-08-11 |
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