CN111213251B - organic light emitting diode - Google Patents

organic light emitting diode Download PDF

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CN111213251B
CN111213251B CN201980005002.0A CN201980005002A CN111213251B CN 111213251 B CN111213251 B CN 111213251B CN 201980005002 A CN201980005002 A CN 201980005002A CN 111213251 B CN111213251 B CN 111213251B
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group
chemical formula
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CN111213251A (en
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河宰承
李禹哲
李敏宇
文贤真
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LG Chem Ltd
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LG Chem Ltd
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/633—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers

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  • Electroluminescent Light Sources (AREA)

Abstract

The present specification provides an organic light emitting device, including: a first electrode, a second electrode provided opposite to the first electrode, and a first organic layer and a second organic layer provided between the first electrode and the second electrode, wherein the first organic layer contains a compound represented by chemical formula 1, and the second organic layer contains a compound represented by chemical formula 2 or chemical formula 3.

Description

Organic light emitting diode
Technical Field
The present application claims priority from korean patent application No. 10-2018-0024648, filed to the korean patent office on the basis of 28 of 02 of 2018, the entire contents of which are incorporated herein.
The present application relates to an organic light emitting device.
Background
In general, the organic light emitting phenomenon refers to a phenomenon of converting electric energy into light energy using an organic substance. An organic light emitting device using an organic light emitting phenomenon generally has a structure including an anode and a cathode and an organic layer therebetween. Here, in order to improve efficiency and stability of the organic light-emitting device, the organic layer is often formed of a multilayer structure composed of different substances, and may be formed of, for example, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, or the like. With the structure of such an organic light emitting device, if a voltage is applied between both electrodes, holes are injected from the anode to the organic layer, electrons are injected from the cathode to the organic layer, excitons (exiton) are formed when the injected holes and electrons meet, and light is emitted when the excitons re-transition to the ground state.
There is a continuing need to develop new materials for use in organic light emitting devices as described above.
Disclosure of Invention
Technical problem
The application provides an organic light emitting device.
Solution to the problem
The present application provides an organic light emitting device, wherein the organic light emitting device comprises: a first electrode, a second electrode disposed opposite to the first electrode, and a first organic layer and a second organic layer disposed between the first electrode and the second electrode,
the first organic layer includes a compound represented by the following chemical formula 1,
the second organic layer includes a compound represented by chemical formula 2 or chemical formula 3.
[ chemical formula 1]
In the chemical formula 1, the chemical formula is shown in the drawing,
l1 to L3 are each independently a direct bond, or a substituted or unsubstituted arylene group,
ar1 to Ar3 are each independently hydrogen, deuterium, or a substituted or unsubstituted aryl group,
r1 and R2 are each independently hydrogen, deuterium, a halogen group, cyano, nitro, substituted or unsubstituted alkyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted haloalkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted aryl, or substituted or unsubstituted heterocyclyl,
a and b are each independently integers from 0 to 4,
a and b are each independently 2 or more, the substituents in parentheses are the same or different from each other,
[ chemical formula 2]
In the chemical formula 2, the chemical formula is shown in the drawing,
l4 and L5 are each independently a direct bond, or a substituted or unsubstituted arylene group,
ar4 and Ar5 are each independently a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group,
at least one of Ar4 and Ar5 is a substituted or unsubstituted aryl group having 10 to 60 carbon atoms,
r3 and R4 are each independently hydrogen, deuterium, a halogen group, cyano, nitro, substituted or unsubstituted alkyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted haloalkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted aryl, or substituted or unsubstituted heterocyclyl,
c and d are each independently integers from 0 to 4,
c and d are each independently 2 or more, the substituents in parentheses are the same or different from each other,
[ chemical formula 3]
In the chemical formula 3, the chemical formula is shown in the drawing,
l6 to L8 are each independently a direct bond, or a substituted or unsubstituted arylene group,
ar6 through Ar8 are each independently hydrogen, deuterium, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group,
R5 and R6 are each independently hydrogen, deuterium, a halogen group, cyano, nitro, substituted or unsubstituted alkyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted haloalkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted aryl, or substituted or unsubstituted heterocyclyl,
e and f are each independently integers from 0 to 4,
e and f are each independently 2 or more, the substituents in parentheses are the same or different from each other.
Effects of the application
An organic light emitting device using the compound according to an embodiment of the present application can achieve low driving voltage, high light emitting efficiency, or long life.
Drawings
Fig. 1 illustrates an example of an organic light emitting device in which a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4 are sequentially stacked.
Fig. 2 illustrates an example of an organic light-emitting device in which a substrate 1, an anode 2, a first hole-regulating layer 5, a second hole-regulating layer 6, a light-emitting layer 3, an electron-transporting layer 7, and a cathode 4 are stacked in this order.
Fig. 3 illustrates an example of an organic light-emitting device in which a substrate 1, an anode 2, a hole injection layer 8, a hole transport layer 9, a hole adjustment layer 10, a light-emitting layer 3, an electron adjustment layer 11, an electron transport layer 7, and a cathode 4 are stacked in this order.
Fig. 4 illustrates an example of an organic light-emitting device in which a substrate 1, an anode 2, a hole injection layer 8, a hole transport layer 9, a first hole adjustment layer 5, a second hole adjustment layer 6, a light-emitting layer 3, an electron adjustment layer 11, an electron transport layer 7, and a cathode 4 are stacked in this order.
1: substrate board
2: anode
3: light-emitting layer
4: cathode electrode
5: a first hole regulating layer
6: a second hole adjusting layer
7: electron transport layer
8: hole injection layer
9: hole transport layer
10: hole regulating layer
11: electronic regulating layer
Detailed Description
The present specification will be described in more detail below.
The present application provides an organic light emitting device, wherein the organic light emitting device comprises: a first electrode, a second electrode provided opposite to the first electrode, and a first organic layer and a second organic layer provided between the first electrode and the second electrode, wherein the first organic layer contains a compound represented by the following chemical formula 1, and the second organic layer contains a compound represented by the following chemical formula 2 or 3.
According to an embodiment of the present application, the compound represented by the above chemical formula 1 has a core structure as shown above, thereby having an advantage that triplet energy can be adjusted, and can exhibit long life and high efficiency characteristics when used as a compound of each host.
In the present specification, examples of the substituents are described below, but are not limited thereto.
The term "substituted" means that a hydrogen atom bonded to a carbon atom of a compound is replaced with another substituent, and the substituted position is not limited as long as it is a position where a hydrogen atom can be substituted, that is, a position where a substituent can be substituted, and when 2 or more substituents are substituted, 2 or more substituents may be the same or different from each other.
In the present specification, the term "substituted or unsubstituted" means substituted with 1 or more substituents selected from hydrogen, halogen groups, nitrile groups, nitro groups, hydroxyl groups, substituted or unsubstituted alkyl groups, substituted or unsubstituted cycloalkyl groups, substituted or unsubstituted alkenyl groups, substituted or unsubstituted amine groups, substituted or unsubstituted aryl groups, and substituted or unsubstituted heterocyclic groups, or substituted with 2 or more substituents selected from the above-exemplified substituents, or does not have any substituent. For example, the "substituent in which 2 or more substituents are linked" may be a biphenyl group. That is, biphenyl may be aryl or may be interpreted as a substituent in which 2 phenyl groups are linked.
In the present specification, examples of the halogen group include fluorine, chlorine, bromine and iodine.
In the present specification, the number of carbon atoms of the ester group is not particularly limited, but is preferably 1 to 50. Specifically, the compound 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 carbonyl group is not particularly limited, but the number of carbon atoms is preferably 1 to 50. Specifically, the compound may have the following structure, but is not limited thereto.
In the present specification, the alkyl group may be a straight chain or branched chain, and the number of carbon atoms is not particularly limited, but is preferably 1 to 60. Specific examples thereof 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-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-ethylpropyl, 1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl and the like, but are not limited thereto.
In the present specification, cycloalkyl is not particularly limited, but cycloalkyl having 3 to 60 carbon atoms is preferable, and specifically, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2, 3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2, 3-dimethylcyclohexyl, 3,4, 5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl and the like are included, but the present invention is not limited thereto.
In the present specification, the above-mentioned alkoxy group may be a straight chain, branched or cyclic. The carbon number of the alkoxy group is not particularly limited, but is preferably 1 to 20. Specifically, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentoxy, neopentoxy, isopentoxy, n-hexoxy, 3-dimethylbutoxy, 2-ethylbutoxy, n-octoxy, n-nonoxy, n-decyloxy, benzyloxy, p-methylbenzyloxy and the like are possible, but not limited thereto.
In the present specification, the alkenyl group may be a straight chain or branched chain, and the number of carbon atoms is not particularly limited, but is preferably an alkenyl group of 2 to 40. 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-phenylene1-yl, 2-diphenylethylene1-yl, 2-phenyl-2- (naphthalen-1-yl) ethylene1-yl, 2-bis (diphenyl-1-yl) ethylene1-yl, stilbene, styryl and the like, but are not limited thereto.
In the present specification, when the aryl group is a monocyclic aryl group, the number of carbon atoms is not particularly limited, but is preferably 6 to 25. Specifically, the monocyclic aryl group may be phenyl, biphenyl, terphenyl, or the like, but is not limited thereto.
When the aryl group is a polycyclic aryl group, the number of carbon atoms is not particularly limited, but is preferably 10 to 24. Specifically, the polycyclic aryl group may be naphthyl, anthryl, phenanthryl, pyrenyl, perylenyl,Fluorenyl, and the like, but is not limited thereto.
In the present specification, the above fluorenyl group may be substituted, and adjacent substituents may be bonded to each other to form a ring.
In the case where the fluorenyl group is substituted, it may be thatAndetc. However, the present invention is not limited thereto.
In this specification, a heterocyclic group contains one or more non-carbon atoms, i.e., hetero atoms, and specifically, the hetero atoms may contain one or more atoms selected from O, N, se, S and the like. The number of carbon atoms of the heterocyclic group is not particularly limited, and the number of carbon atoms is preferably 2 to 60. Examples of the heterocyclic group include thienyl, furyl, pyrrolyl, imidazolyl, thiazolyl, and the like,Azolyl, (-) -and (II) radicals>Diazolyl, triazolyl, pyridyl, bipyridyl, pyrimidinyl, triazinyl, triazolyl, acridinyl, pyridazinyl, pyrazinyl, quinolinyl, quinazolinyl, quinoxalinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, pyrazinopyrazinyl, isoquinolinyl, indolyl, carbazolyl, benzo- >Oxazolyl, benzimidazolyl, benzothiazolyl, benzocarbazolyl, benzothienyl, dibenzothiophenyl, benzofuranyl, phenanthroline (phenanthrinyl), thiazolyl, and iso ∈>Azolyl, (-) -and (II) radicals>Diazolyl, thiadiazolyl, benzothiazolyl, phenothiazinyl, dibenzofuranyl, and the like, but are not limited thereto.
In one embodiment of the present application, each of the above-mentioned L1 to L3 is an arylene group having 6 to 60 carbon atoms, which is directly bonded or substituted or unsubstituted.
In one embodiment of the present application, each of the above-mentioned L1 to L3 is an arylene group having 6 to 30 carbon atoms, which is directly bonded or substituted or unsubstituted.
In one embodiment of the present application, each of the above L1 to L3 is a direct bond, phenylene, biphenylene, terphenylene, 1-naphthylene or 2-naphthylene.
In one embodiment of the present application, each of Ar1 to Ar3 is independently hydrogen, deuterium, or a substituted or unsubstituted aryl group having 6 to 60 carbon atoms.
In one embodiment of the present application, each of Ar1 to Ar3 is independently hydrogen, deuterium, or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms. In one embodiment of the present application, each of Ar1 to Ar3 is independently hydrogen, deuterium, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted phenanthryl group, or a substituted or unsubstituted triphenylene group.
In one embodiment of the present application, each of Ar1 to Ar3 is independently hydrogen, deuterium, phenyl, biphenyl, terphenyl, fluorenyl, phenanthryl, or triphenylenyl.
In one embodiment of the present application, each of R1 and R2 is independently hydrogen, deuterium, substituted or unsubstituted alkyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted haloalkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted aryl, or substituted or unsubstituted heterocyclyl.
In one embodiment of the present application, each of R1 and R2 is independently hydrogen, deuterium, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group.
In one embodiment of the present application, each of R1 and R2 is independently hydrogen, deuterium, a substituted or unsubstituted aryl group having 6 to 60 carbon atoms, or a substituted or unsubstituted heterocyclic group having 2 to 60 carbon atoms.
In one embodiment of the present application, each of R1 and R2 is independently hydrogen, deuterium, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted heterocyclic group having 2 to 30 carbon atoms.
In one embodiment of the present application, each of R1 and R2 is independently hydrogen or deuterium.
In one embodiment of the present application, each of the above L4 and L5 is independently a directly bonded or substituted or unsubstituted arylene group having 6 to 60 carbon atoms.
In one embodiment of the present application, each of the above L4 and L5 is independently a directly bonded or substituted or unsubstituted arylene group having 6 to 30 carbon atoms.
In one embodiment of the present application, each of the L4 and L5 is independently a direct bond, phenylene, biphenylene, terphenylene, 1-naphthylene or 2-naphthylene.
In one embodiment of the present application, ar4 and Ar5 are each independently hydrogen, deuterium, a substituted or unsubstituted aryl group having 6 to 60 carbon atoms, or a substituted or unsubstituted heterocyclic group having 2 to 60 carbon atoms.
In one embodiment of the present application, ar4 and Ar5 are each independently hydrogen, deuterium, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted heterocyclic group having 2 to 30 carbon atoms.
In one embodiment of the present application, ar4 and Ar5 are each independently hydrogen, deuterium, phenyl, biphenyl, terphenyl, fluorenyl, phenanthryl, triphenylenyl, dibenzofuranyl, dibenzothiophenyl, or carbazolyl.
In one embodiment of the present application, at least one of Ar4 and Ar5 is a substituted or unsubstituted aryl group having 10 to 60 carbon atoms.
In one embodiment of the present application, at least one of Ar4 and Ar5 is a substituted or unsubstituted aryl group having 10 to 30 carbon atoms.
In one embodiment of the present application, ar4 and Ar5 are each a substituted or unsubstituted aryl group, except that Ar4 and Ar5 are each phenyl.
In one embodiment of the present application, each of R3 and R4 is independently hydrogen, deuterium, substituted or unsubstituted alkyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted haloalkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted aryl, or substituted or unsubstituted heterocyclyl.
In one embodiment of the present application, each of R3 and R4 is independently hydrogen, deuterium, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group.
In one embodiment of the present application, each of R3 and R4 is independently hydrogen, deuterium, a substituted or unsubstituted aryl group having 6 to 60 carbon atoms, or a substituted or unsubstituted heterocyclic group having 2 to 60 carbon atoms.
In one embodiment of the present application, each of R3 and R4 is independently hydrogen, deuterium, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted heterocyclic group having 2 to 30 carbon atoms.
In one embodiment of the present application, each of R3 and R4 is independently hydrogen or deuterium.
In one embodiment of the present application, each of the above-mentioned L6 to L8 is an arylene group having 6 to 60 carbon atoms which is directly bonded or substituted or unsubstituted.
In one embodiment of the present application, each of the above-mentioned L6 to L8 is an arylene group having 6 to 30 carbon atoms, which is directly bonded or substituted or unsubstituted.
In one embodiment of the present application, each of the above L6 to L8 is a direct bond, phenylene, biphenylene, terphenylene, 1-naphthylene or 2-naphthylene.
In one embodiment of the present application, each of Ar6 to Ar8 is independently hydrogen, deuterium, a substituted or unsubstituted aryl group having 6 to 60 carbon atoms, or a substituted or unsubstituted heterocyclic group having 2 to 60 carbon atoms.
In one embodiment of the present application, each of Ar6 to Ar8 is independently hydrogen, deuterium, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted heterocyclic group having 2 to 30 carbon atoms.
In one embodiment of the present application, each of Ar6 to Ar8 is independently hydrogen, deuterium, phenyl, biphenyl, terphenyl, fluorenyl, phenanthryl, triphenylenyl, dibenzofuranyl, dibenzothiophenyl or carbazolyl.
In one embodiment of the present application, each of R5 and R6 is independently hydrogen, deuterium, substituted or unsubstituted alkyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted haloalkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted aryl, or substituted or unsubstituted heterocyclyl.
In one embodiment of the present application, each of R5 and R6 is independently hydrogen, deuterium, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group.
In one embodiment of the present application, each of R5 and R6 is independently hydrogen, deuterium, a substituted or unsubstituted aryl group having 6 to 60 carbon atoms, or a substituted or unsubstituted heterocyclic group having 2 to 60 carbon atoms.
In one embodiment of the present application, each of R5 and R6 is independently hydrogen, deuterium, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted heterocyclic group having 2 to 30 carbon atoms.
In one embodiment of the present application, each of R5 and R6 is independently hydrogen or deuterium.
In one embodiment of the present application, the chemical formula 1 is selected from the following structural formulas.
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In an embodiment of the application, the chemical formula 2 is selected from the following structural formulas.
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In one embodiment of the present application, the chemical formula 3 is selected from the following structural formulas.
In the present application, when it is noted that a certain member is "on" another member, it includes not only the case where the certain member is in contact with the other member but also the case where the other member is present between the two members.
In the present application, when a certain component is indicated as being "included" in a certain section, unless otherwise stated, it means that other components may be further included, and not excluded.
The first and second organic layers of the organic light emitting device of the present application may be formed of a single layer structure, or may be formed of a multilayer structure in which 2 or more organic layers are stacked. For example, the first organic layer of the present application may be composed of 1 to 3 layers. Further, the organic light emitting device of the present application may have a structure including a hole injection layer, a light emitting layer, an electron transport layer, and the like as the organic layer. However, the structure of the organic light emitting device is not limited thereto, and may include a greater or lesser number of organic layers.
In an embodiment of the present application, the organic light emitting device further includes 1 layer or more than 2 layers selected from a hole injection layer, a hole transport layer, an electron injection layer, an electron blocking layer, and a hole blocking layer.
In one embodiment of the present application, the organic light emitting device includes: a first electrode; a second electrode provided opposite to the first electrode; and a light-emitting layer provided between the first electrode and the second electrode; and a first and second organic layers having 2 or more layers between the light-emitting layer and the first electrode or between the light-emitting layer and the second electrode, wherein the first and second organic layers having 2 or more layers each contain a compound represented by chemical formula 1 and a compound represented by chemical formula 2 or 3.
In one embodiment of the present application, the first organic layer may include a hole adjusting layer, and the hole adjusting layer may include a compound represented by chemical formula 1.
In one embodiment of the present application, the first organic layer may include 2 or more hole-regulating layers, and at least one of the 2 or more hole-regulating layers may include a compound represented by chemical formula 1.
In addition, according to an embodiment of the present application, the second organic layer includes a light emitting layer, and the light emitting layer may include a compound represented by chemical formula 2 or 3.
In an embodiment of the application, the light emitting layer is a blue light emitting layer.
In an embodiment of the present application, the organic light emitting device further includes 1 layer or more than 2 layers selected from a hole injection layer, a hole transport layer, an electron injection layer, an electron blocking layer, and a hole blocking layer.
In one embodiment of the present application, the organic light emitting device includes: a first electrode; a second electrode provided opposite to the first electrode; and a light-emitting layer provided between the first electrode and the second electrode; and a first or second organic layer having 2 or more layers between the light-emitting layer and the first electrode or between the light-emitting layer and the second electrode, wherein at least one of the first or second organic layers having 2 or more layers contains the compound.
In one embodiment of the present application, the first organic layer may include 2 or more hole-regulating layers, and at least one of the 2 or more hole-regulating layers may be disposed in contact with the second organic layer.
In one embodiment of the present application, the second organic layer includes 2 or more light-emitting layers, and at least one of the 2 or more light-emitting layers includes a compound represented by chemical formula 2 or 3. Specifically, in one embodiment of the present application, the compound may be contained in 1 of the 2 or more light-emitting layers, or may be contained in each of the 2 or more light-emitting layers.
In addition, in an embodiment of the present application, when the above-described compound is contained in each of the light-emitting layers of 2 or more layers, materials other than the above-described compound may be the same as or different from each other.
In one embodiment of the present application, the organic layer further includes a hole injection layer or a hole transport layer including a compound including an arylamino group, a carbazole group, or a benzocarbazole group, in addition to the organic layer including the compound.
In another embodiment, the organic light emitting device may be a structure (normal type) in which an anode, 1 or more organic layers, and a cathode are sequentially stacked on a substrate.
In another embodiment, the organic light emitting device may be an inverted (inverted type) organic light emitting device in which a cathode, 1 or more organic layers, and an anode are sequentially stacked on a substrate.
For example, a structure of an organic light emitting device according to an embodiment of the present application is illustrated in fig. 1 and 2.
Fig. 1 illustrates a structure of a general organic light emitting device in which a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4 are sequentially stacked.
Fig. 2 illustrates a structure of an organic light emitting device in which a substrate 1, an anode 2, a first hole adjusting layer 5, a second hole adjusting layer 6, a light emitting layer 3, an electron transporting layer 7, and a cathode 4 are sequentially stacked. In this structure, the compound represented by the above chemical formula 1 may be contained in the above second hole adjusting layer 6, and the compound represented by the above chemical formula 2 or 3 may be contained in the light emitting layer 3.
Fig. 3 illustrates a structure of an organic light emitting device in which a substrate 1, an anode 2, a hole injection layer 8, a hole transport layer 9, a hole adjustment layer 10, a light emitting layer 3, an electron adjustment layer 11, an electron transport layer 7, and a cathode 4 are stacked in this order. In this structure, the compound represented by the above chemical formula 1 may be contained in the above hole adjusting layer 10, and the compound represented by the above chemical formula 2 or 3 may be contained in the light emitting layer 3.
Fig. 4 illustrates a structure of an organic light emitting device in which a substrate 1, an anode 2, a hole injection layer 8, a hole transport layer 9, a first hole adjustment layer 5, a second hole adjustment layer 6, a light emitting layer 3, an electron adjustment layer 11, an electron transport layer 7, and a cathode 4 are sequentially stacked. In this structure, the compound represented by the above chemical formula 1 may be contained in the above second hole adjusting layer 6, and the compound represented by the above chemical formula 2 or 3 may be contained in the light emitting layer 3.
In the organic light-emitting device of the present application, one or more of the first or second organic layers contains the compound of the present application, that is, the above-described compound, but can be produced by materials and methods well known in the art.
When the organic light emitting device includes a plurality of first or second organic layers, the organic layers may be formed of the same material or different materials.
In the organic light-emitting device of the present application, one or more of the first or second organic layers may be manufactured using materials and methods well known in the art, except that the above-described compound, that is, the compound represented by any one of the above-described chemical formulas 1 to 3, is included.
For example, the organic light emitting device of the present application may be manufactured by sequentially stacking a first electrode, first and second organic layers, and a second electrode on a substrate. At this time, it can be manufactured as follows: PVD (physical vapor deposition) such as sputtering (sputtering) or electron beam evaporation (physical vapor deposition) is used to deposit a metal or a metal oxide having conductivity or an alloy thereof on a substrate to form an anode, then an organic 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 substance that can be used as a cathode is deposited on the organic layer. In addition to this method, an organic light-emitting device may be manufactured by sequentially depositing a cathode material, an organic layer, and an anode material on a substrate.
In addition, the compounds of the chemical formulas 1 to 3 may be used not only in the vacuum evaporation method but also in the solution coating method to form the organic layer in the production of the organic light-emitting device. Here, the solution coating method refers to spin coating, dip coating, blade coating, inkjet printing, screen printing, spray coating, roll coating, and the like, but is not limited thereto.
In addition to this method, an organic light-emitting device can be manufactured by sequentially depositing a cathode material, an organic layer, and an anode material on a substrate (international patent application publication No. 2003/012890). However, the manufacturing method is not limited thereto.
In one embodiment of the present application, the first electrode is an anode, and the second electrode is a cathode.
In another embodiment, the first electrode is a cathode, and the second electrode is an anode.
The anode material is preferably a material having a large work function so that holes can be smoothly injected into the first or second organic layer. Specific examples of the anode material that can be used in the present application include metals such as vanadium, chromium, copper, zinc, gold, and the like, or alloys thereof; metal oxides such as zinc oxide, indium Tin Oxide (ITO), and Indium Zinc Oxide (IZO); znO of Al or SnO 2 A combination of metals such as Sb and the like and oxides; poly (3-methylthiophene), poly [3,4- (ethylene-1, 2-dioxy) thiophene]Conductive polymers such as (PEDOT), polypyrrole and polyaniline, but not limited thereto.
As the cathode material, a material having a small work function is generally preferred in order to facilitate electron injection. Specific examples of the cathode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, and alloys thereof; liF/Al or LiO 2 And/or Al, but is not limited thereto.
The hole injection layer is a layer that injects holes from an electrode, and the following compounds are preferable as the hole injection substance: the light-emitting device has a hole transporting capability, a hole injecting effect from an anode, an excellent hole injecting effect for a light-emitting layer or a light-emitting material, prevention of migration of excitons generated in the light-emitting layer to the electron injecting layer or the electron injecting material, and an excellent thin film forming capability. The HOMO (highest occupied molecular orbital ) of the hole-injecting substance is preferably between the work function of the anode substance and the HOMO of the surrounding organic layer. Specific examples of the hole injection substance include, but are not limited to, metalloporphyrin (porphyrin), oligothiophenes, arylamine-based organic substances, hexanitrile hexaazabenzophenanthrene-based organic substances, quinacridone-based organic substances, perylene-based organic substances, anthraquinones, polyaniline and polythiophene-based conductive polymers.
The hole-transporting layer is a layer that receives holes from the hole-injecting layer and transports the holes to the light-emitting layer, and a hole-transporting substance that can receive holes from the anode or the hole-injecting layer and transfer the holes to the light-emitting layer is preferable, and a substance having a large mobility to the holes is preferable. Specific examples include, but are not limited to, arylamine-based organic substances, conductive polymers, and block copolymers having both conjugated and unconjugated portions.
The light-emitting substance is a substance capable of receiving holes and electrons from the hole-transporting layer and the electron-transporting layer, respectively, and combining them to emit light in the visible light region, and preferably has high quantum efficiency for fluorescence or phosphorescence. Specific examples thereof include 8-hydroxyquinoline aluminum complex (Alq 3); carbazole-based compounds; dimeric styryl (dimerized styryl) compounds; BAlq; 10-hydroxybenzoquinoline metal compounds; benzo (E) benzo (EAzole, benzothiazole, and benzimidazole compounds; poly (p-phenylene vinylene) (PPV) based polymers; spiro (spiro) compounds; polyfluorene, rubrene, and the like, but is not limited thereto.
The electron transporting layer is a layer that receives electrons from the electron injecting layer and transports the electrons to the light emitting layer, and the electron transporting substance is a substance that can well inject electrons from the cathode and transfer the electrons to the light emitting layer, and is preferably a substance having high mobility for electrons. Specific examples include, but are not limited to, al complexes of 8-hydroxyquinoline, complexes containing Alq3, organic radical compounds, hydroxyflavone-metal complexes, and the like. The electron transport layer may be used with any desired cathode material as used in the art. In particular, examples of suitable cathode materials are the usual materials having a low work function accompanied by an aluminum layer or a silver layer. In particular cesium, barium, calcium, ytterbium and samarium, in each case accompanied by an aluminum layer or a silver layer.
The electron injection layer is a layer that injects electrons from an electrode, and the electron injection material is preferably the following compound: has an electron transporting ability, an electron injecting effect from a cathode, an excellent electron injecting effect to a light emitting layer or a light emitting material, prevents excitons generated in the light emitting layer from migrating to a hole injecting layer, and has an excellent thin film forming ability. Specifically, fluorenone, anthraquinone dimethane, diphenoquinone, thiopyran dioxide, and the like,Azole,/->Diazole, triazole, imidazole, perylene tetracarboxylic acid, fluorenylmethylene +.>Anthrone and the like, and derivatives thereof, metal complex compounds, nitrogen-containing five-membered ring derivatives and the like, but are not limited thereto.
Examples of the metal complex 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 (10-hydroxybenzo [ h ] quinoline), gallium chloride bis (2-methyl-8-quinoline) (o-cresol) gallium, aluminum bis (2-methyl-8-quinoline) (1-naphthol), gallium bis (2-methyl-8-quinoline) (2-naphthol).
The hole blocking layer is a layer that blocks holes from reaching the cathode, and can be formed under the same conditions as the hole injection layer. Specifically, there areThe diazole derivative, triazole derivative, phenanthroline derivative, BCP, aluminum complex (aluminum complex), and the like, but are not limited thereto.
The organic light emitting device according to the present application may be of a top emission type, a bottom emission type, or a bi-directional emission type, depending on the materials used.
EMBODIMENTS FOR CARRYING OUT THE INVENTION
Regarding the manufacture of the organic light emitting device including the compounds represented by the above chemical formulas 1 to 3, description is specifically made in the following examples. However, the following examples are given by way of illustration of the present specification, and the scope of the present specification is not limited thereto.
Preparation example 1 (Synthesis of chemical formula 1)
Synthesis of Compound 1-1
9-bromophenanthrene (15 g,39.55 mmol), N- ([ 1,1' -biphenyl ] -4-yl) -9, 9-diphenyl-9H-fluoren-2-amine (12.96 g,40.34 mmol), sodium t-butoxide (5.3, 55.37 mol) were added to xylene, heated and stirred, and then refluxed with [ bis (tri-t-butylphosphine) ] palladium (404 mg,2 mmol%) being added. After completion of the reaction, the temperature was lowered to room temperature, and then recrystallized from tetrahydrofuran and ethyl acetate, whereby compound 1-1 (19.6 g, 82%) was produced.
MS[M+H] + ＝662.85
Synthesis of Compounds 1-2
Compound 1-2 was synthesized by the same method except that N- ([ 1,1 '-diphenyl ] -4-yl) -9, 9-dimethyl-9H-fluoren-2-amine was used instead of N- ([ 1,1' -biphenyl ] -4-yl) -9, 9-diphenyl-9H-fluoren-2-amine in the synthesis of the above compound 1-1.
MS[M+H] + ＝538.71
Synthesis of Compounds 1-3
Compound 1-3 was synthesized by the same method except that N- (4- (dimethyl-9H-fluoren-1-yl) phenyl) - [1,1 '-biphenyl ] -4-amine was used instead of N- ([ 1,1' -biphenyl ] -4-yl) -9, 9-diphenyl-9H-fluoren-2-amine in the synthesis of the above compound 1-1.
MS[M+H] + ＝588.72
Synthesis of Compounds 1-4
Compound 1-4 was synthesized by the same method except that N- (4- (naphthalen-1-yl) phenyl) - [1,1 '-biphenyl ] -4-amine was used instead of N- ([ 1,1' -biphenyl ] -4-yl) -9, 9-diphenyl-9H-fluoren-2-amine in the synthesis of the above compound 1-1.
MS[M+H] + ＝548.70
Synthesis of Compounds 1-5 to 1-7
● Synthesis of A1
After 9-bromophenanthrene (20 g,52.7 mmol) and 4-chlorophenylboronic acid (8.66 g,55.3 mmol) were added to tetrahydrofuran (300 ml), a 2M aqueous potassium carbonate solution (150 ml) was added, and tetrakis (triphenylphosphine) palladium (1.21 g,2 mol%) was added thereto, followed by stirring under heating for 10 hours. The temperature was lowered to room temperature, and after the reaction was completed, the aqueous potassium carbonate solution was removed to separate the layers. After the solvent was removed, the white solid was recrystallized from ethyl acetate, whereby the above-mentioned A1 (19.48 g, yield 90%) was produced.
MS[M+H] + ＝289.77
● Synthesis of Compounds 1-5
In the synthesis of the above compound 1-1, the same procedure was repeated except that A1 was used instead of 9-bromophenanthrene, and N- ([ 1,1 '-diphenyl ] -4-yl) -9, 9-dimethyl-9H-fluoren-2-amine was used instead of N- ([ 1,1' -biphenyl ] -4-yl) -9, 9-diphenyl-9H-fluoren-2-amine, to thereby produce compound 1-5.
MS[M+H] + ＝614.80
● Synthesis of Compounds 1-6
In the synthesis of the above compound 1-1, the same procedure was followed except that A1 was used instead of 9-bromophenanthrene and 2-aminobiphenyl was used instead of N- ([ 1,1' -biphenyl ] -4-yl) -9, 9-diphenyl-9H-fluoren-2-amine, to thereby prepare compound 1-6.
MS[M+H] + ＝674.86
● Synthesis of Compounds 1-7
In the synthesis of the above compound 1-1, the same procedure was followed except that A1 was used instead of 9-bromophenanthrene and 9, 9-dimethyl-9H-fluoren-2-amine was used instead of N- ([ 1,1' -biphenyl ] -4-yl) -9, 9-diphenyl-9H-fluoren-2-amine, to thereby prepare compound 1-7.
MS[M+H] + ＝714.92
Synthesis of Compounds 1-8
● Synthesis of A2
Compound A2 was synthesized by the same method except that 3-chlorophenylboronic acid was used instead of 4-chlorophenylboronic acid in the synthesis of compound A1.
MS[M+H] + ＝289.77
● Synthesis of Compounds 1-8
In the synthesis of the above compound 1-1, the same procedure was repeated except that A2 was used in place of 9-bromophenanthrene and N- (1, 1 '-biphenyl) -2-yl) - [1,1':4',1 "-terphenyl ] -4-amine was used in place of N- ([ 1,1' -biphenyl ] -4-yl) -9, 9-diphenyl-9H-fluoren-2-amine, to thereby produce compound 1-8.
MS[M+H] + ＝650.84
Synthesis of Compounds 1-9
● Synthesis of A3
Compound A3 was synthesized by the same method except that 4-bromo-N-phenylaniline was used instead of 9-bromophenanthrene and triphenylene-2-ylboronic acid was used instead of 4-chlorophenylboronic acid in the synthesis of A1.
MS[M+H] + ＝396.51
● Synthesis of Compounds 1-9
In the synthesis of the above compound 1-1, the same procedure was followed except that A1 was used instead of 9-bromophenanthrene and A3 was used instead of N- ([ 1,1' -biphenyl ] -4-yl) -9, 9-diphenyl-9H-fluoren-2-amine, to prepare compound 1-9.
MS[M+H] + ＝648.82
Synthesis of Compounds 1-10 to 1-12
● Synthesis of A4 to A5
● Synthesis of int.1
Compound int.1 was produced by the same method as in the synthesis of A1 above except that 9-bromo-10-hydroxyphenanthrene was used instead of 9-bromophenanthrene and phenylboronic acid was used instead of 4-chlorophenylboronic acid.
MS[M+H] + ＝271.33
● Synthesis of int.2
The above compound int.1 (15 g,33.89 mmol) and potassium carbonate (7.0 g,50.7 mmol) were added to Acrylonitrile (AN) (200 ml), H 2 O (50 ml) and stirred, then perfluorobutylsulfonyl fluoride (13.3)g,44.05 mmol). After removal of the solvent by extraction with ethyl acetate and water, recrystallization from tetrahydrofuran and ethyl acetate produced int.2 (10.84 g, 75%).
MS[M+H] + ＝553.41
● Synthesis of A4
Compound A4 was synthesized by the same method except that int.2 was used instead of 9-bromophenanthrene in the synthesis of A1.
MS[M+H] + ＝365.87
● Synthesis of A5
Compound A5 was synthesized by the same method except that int.2 was used instead of 9-bromophenanthrene and 3-chlorophenyl boric acid was used instead of 4-chlorophenyl boric acid in the synthesis of A1.
MS[M+H] + ＝365.87
● Synthesis of Compounds 1-10
In the synthesis of the above compound 1-1, the same procedure was followed except that A4 was used instead of 9-bromophenanthrene and di ([ 1,1 '-biphenyl ] -4-yl) amine was used instead of N- ([ 1,1' -biphenyl ] -4-yl) -9, 9-diphenyl-9H-fluoren-2-amine, to thereby prepare compound 1-10.
MS[M+H] + ＝650.84
● Synthesis of Compounds 1-11
In the synthesis of the above compound 1-1, the same procedure was repeated except that A4 was used instead of 9-bromophenanthrene, N- ([ 1,1 '-diphenyl ] -4-yl) -9, 9-dimethyl-9H-fluoren-2-amine was used instead of N- ([ 1,1' -biphenyl ] -4-yl) -9, 9-diphenyl-9H-fluoren-2-amine, and compound 1-11 was produced.
MS[M+H] + ＝690.90
● Synthesis of Compounds 1-12
In the synthesis of the above compound 1, compounds 1 to 12 were synthesized by the same method except that A5 was used instead of 9-bromophenanthrene and di ([ 1,1 '-biphenyl ] -4-yl) amine was used instead of N- ([ 1,1' -biphenyl ] -4-yl) -9, 9-diphenyl-9H-fluoren-2-amine.
MS[M+H] + ＝650.84
Synthesis of Compounds 1-13
Compounds 1 to 13 were synthesized by the same method except that 9-phenanthreneboronic acid was used instead of 9-bromophenanthrene and N, N-bis (4-bromophenyl) - [1,1' -biphenyl ] -4-amine was used instead of 4-chlorophenyl boronic acid in the synthesis of A1.
MS[M+H] + ＝674.86
Preparation example 2 (Synthesis of chemical formula 2)
● Synthesis of Compounds 2-1 to 2-11
Synthesis of Compound 2-1
9-bromo-10-phenylanthracene (10 g,30.1 mmol) and (4-phenylnaphthalen-1-yl) boronic acid (9 g,36.1 mmol), pd (t-Bu 3P) 2 (0.8 g,0.15 mmol) were added to a 2M aqueous potassium carbonate solution (30 mL) and THF (100 mL) and stirred at reflux for about 12 hours. After completion of the reaction, the mixture was cooled to room temperature, the organic layer was separated from the reaction mixture, dried over magnesium sulfate, distilled under reduced pressure, and recrystallized from Tol/EA to give Compound 2-1 (12.8 g, 93%).
MS[M+H] + ＝457.59
Synthesis of Compound 2-2
Compound 2-2 was produced by the same method as the synthesis of 2-1 described above, except that 9- ([ 1,1' -biphenyl ] -4-yl) -10-bromoanthracene was used instead of 9-bromo-10-phenylanthracene.
MS[M+H] + ＝533.69
Synthesis of Compound 2-3
In the above synthesis of 2-1, the compound 2-3 was produced by the same method except that 9-bromo- (10-naphthalen-1-yl) anthracene was used instead of 9-bromo-10-phenylanthracene, and (4- (naphthalen-2-yl) phenyl) boric acid was used instead of (4-phenylnaphthalen-1-yl) boric acid.
MS[M+H] + ＝507.65
Synthesis of Compounds 2-4
Compound 2-4 was produced by the same method as the synthesis of 2-3 above except that ([ 1,1 '-biphenyl ] -4-yl-2', 3',4',5',6' -d 5) boric acid was used instead of (4- (naphthalen-2-yl) phenyl) boric acid.
MS[M+H] + ＝462.62
Synthesis of Compounds 2-5
Compound 2-5 was produced by the same method as that for the synthesis of 2-3 above except that 2-naphthaleneboronic acid was used instead of (4- (naphthalen-2-yl) phenyl) boronic acid.
MS[M+H] + ＝431.55
Synthesis of Compounds 2-6
/>
Compounds 2 to 6 were synthesized by the same method except that (4-phenylnaphthalen-1-yl) boric acid was used instead of (4- (naphthalen-2-yl) phenyl) boric acid in the synthesis of 2 to 3.
MS[M+H] + ＝507.65
Synthesis of Compounds 2-7
Compound 2-7 was synthesized by the same method except that indole [3,2,1-jk ] -carbazol-6-yl boronic acid was used instead of (4- (naphthalen-2-yl) phenyl) boronic acid in the synthesis of 2-3.
MS[M+H] + ＝544.67
Synthesis of Compounds 2-8
In the above synthesis of 2-1, the compound 2-8 was produced by the same method except that 9-bromo- (10-naphthalen-2-yl) anthracene was used instead of 9-bromo-10-phenylanthracene, and (4- (naphthalen-2-yl) phenyl) boric acid was used instead of (4-phenylnaphthalen-1-yl) boric acid.
MS[M+H] + ＝507.65
Synthesis of Compounds 2-9
Compounds 2 to 9 were synthesized by the same method except that 4-biphenylboronic acid was used instead of (4- (naphthalen-2-yl) phenyl) boronic acid in the synthesis of 2 to 8.
MS[M+H] + ＝457.59
Synthesis of Compounds 2-10
Compounds 2 to 10 were synthesized by the same method except that (8-phenylnaphthalen-2-yl) boric acid was used instead of (4- (naphthalen-2-yl) phenyl) boric acid in the synthesis of 2 to 8.
MS[M+H] + ＝507.65
Synthesis of Compounds 2-11
Compounds 2 to 11 were synthesized by the same method except that (3- (5-phenylthiophen-2-yl) phenyl) boronic acid was used instead of (4- (naphthalen-2-yl) phenyl) boronic acid in the synthesis of 2 to 8.
MS[M+H] + ＝539.71
● Synthesis of Compounds 2-12 to 2-13
Synthesis of int.3
1, 8-dichloroanthraquinone (50 g,180 mmol) was dissolved in ammonia (2000L), zinc powder (Zn dur) (1500 g) was added and stirred under reflux. After the completion of the reaction, the reaction mixture was cooled to room temperature and filtered, the organic layer was separated from the reaction filtrate, dried over magnesium sulfate, distilled under reduced pressure, recrystallized from Hexane (Hexane), and the obtained solid was dissolved in isopropyl alcohol, and added with concentrated hydrochloric acid and stirred under reflux for 5 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, and the resultant solid was filtered, washed with water and dried to obtain int.3 (27.8 g, 63%).
MS[M+H] + ＝248.13
● Synthesis of B1 to B5
Synthesis of B1
Int.3 (20 g,80.9 mmol), (3, 5-dimethylphenyl) boronic acid (24.8 g,164.22 mmol), pd (dba) 2 (1.40 g,2.43 mmol), PCy3 (1.36 g,4.86 mmol) was added to 2M K 3 PO 4 Aqueous solution (100 mL) and THF (500 mL) were stirred at reflux for about 12 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, the organic layer was separated from the reaction mixture, dried over magnesium sulfate, distilled under reduced pressure, recrystallized from THF/EtOH, filtered, and the solid was dissolved in chloroform (500 mL), followed by addition of NBS (1 eq) and stirring at room temperature for 12 hours. After completion of the reaction, the solid formed in the reaction was filtered, washed with distilled water and dried to obtain B1 (32 g, 85%).
MS[M+H] + ＝466.43
Synthesis of B2
Compound B2 was produced by the same method as the synthesis of B1 above except that 1-naphthalene boric acid was used instead of (3, 5-dimethylphenyl) boric acid.
MS[M+H] + ＝510.45
Synthesis of B3
Compound B3 was produced by the same method as the synthesis of B1 above except that 2-naphthalene boric acid was used instead of (3, 5-dimethylphenyl) boric acid.
MS[M+H] + ＝510.45
Synthesis of B4
B4 was synthesized by the same method except that [1,1':3',1 "-terphenyl ] -5' -ylboronic acid was used instead of (3, 5-dimethylphenyl) boronic acid in the synthesis of B1 described above.
MS[M+H] + ＝714.72
Synthesis of B5
B5 was synthesized by the same method except that dibenzo [ B, d ] furan-4-ylboronic acid was used instead of (3, 5-dimethylphenyl) boronic acid in the synthesis of B1.
MS[M+H] + ＝590.49
Synthesis of Compounds 2-12
Compound 2-12 was synthesized by the same method except that B1 was used instead of 9-bromo-10-phenylanthracene and 4-biphenylboronic acid was used instead of (4-phenylnaphthalen-1-yl) boronic acid in the synthesis of 2-1.
MS[M+H] + ＝539.73
Synthesis of Compounds 2-13
Compound 2-13 was synthesized by the same method except that B2 was used instead of 9-bromo-10-phenylanthracene and 1-naphthalene boronic acid was used instead of (4-phenylnaphthalen-1-yl) boronic acid in the synthesis of 2-1.
MS[M+H] + ＝557.71
Synthesis of Compounds 2-14
In the synthesis of 2-1 above, B3 was used instead of 9-bromo-10-phenylanthracene, and [1,1'; compound 2-14 was produced by the same method except that 3',1 "-terphenyl ] -5' -ylboronic acid was used instead of (4-phenylnaphthalen-1-yl) boronic acid.
MS[M+H] + ＝659.84
Synthesis of Compounds 2-15
In the above synthesis of 2-1, compound 2-15 was produced by the same method except that B4 was used instead of 9-bromo-10-phenylanthracene and phenylboronic acid was used instead of (4-phenylnaphthalen-1-yl) boronic acid.
MS[M+H] + ＝711.92
Synthesis of Compounds 2-16
Compounds 2 to 16 were synthesized by the same method except that B5 was used instead of 9-bromo-10-phenylanthracene in the synthesis of 2-1 described above.
MS[M+H] + ＝713.85
Example 1
ITO (indium tin oxide) toThe glass substrate (corning 7059 glass) coated in a thin film was put into distilled water in which a detergent was dissolved, and washed with ultrasonic waves. The detergent was a product of fei-hill co., and the distilled water was distilled water filtered twice using a Filter (Filter) manufactured by millbore co., ltd. After washing the ITO for 30 minutes, ultrasonic washing was performed for 10 minutes by repeating twice with distilled water. After the distilled water washing was completed, ultrasonic washing was performed with solvents of isopropyl alcohol, acetone, and methanol in this order, and drying was performed.
In the thus prepared ITO transparentOn the bright electrode, HI-1, hexanitrile hexaazabenzophenanthrene (hexanitrile hexaazatriphenylene) was used as the electrodeAnd performing thermal vacuum evaporation to form a hole injection layer. On the hole injection layer, HT1 +.>After vacuum evaporation, compound 1-1 synthesized in production example 1 was then deposited on the hole transport layer at a film thickness +.>Vacuum deposition is performed to form a hole adjusting layer. As the light-emitting layer, the host compound 2-1 and the dopant BD1 compound (25:1, weight ratio) synthesized in production example 2 were combined in +. >Vacuum evaporation was performed on the thickness of (c). Then, ET 1->After formation as electronic regulating layer ET2 +.>And LiQ was vapor deposited at a weight ratio of 2:1, and thermal vacuum vapor deposition was sequentially performed as an electron transport layer. On the electron transport layer, lithium fluoride (LiF) is added in sequence +.>Thickness of aluminum->The thickness was evaporated to form a cathode, thereby manufacturing an organic light emitting device.
In the above process, the vapor deposition rate of the organic matter is maintainedLithium fluoride is maintained->Is kept at>Is a vapor deposition rate of (a). />
With respect to examples 1 to 52 and comparative examples 1 to 6, experiments were conducted on organic light-emitting devices manufactured using the respective compounds synthesized in manufacturing examples 1 and 2 as hole-regulating layers and host substances, and the results thereof, i.e., examples 1 to 52 and comparative examples 1 to 6, are shown in tables 1 to 3 below.
TABLE 1
TABLE 2
TABLE 3
Example 53
ITO (indium tin oxide) toThe glass substrate (corning 7059 glass) coated in a thin film was put into distilled water in which a detergent was dissolved, and washed with ultrasonic waves. The detergent was a product of fei-hill company (Fischer co.), and distilled water was a product manufactured by millbore co., ltdIs filtered twice with a Filter (Filter). After washing the ITO for 30 minutes, ultrasonic washing was performed for 10 minutes by repeating twice with distilled water. After the distilled water washing was completed, ultrasonic washing was performed with solvents of isopropyl alcohol, acetone, and methanol in this order, and drying was performed.
On the ITO transparent electrode thus prepared, HI-1, hexanitrile hexaazabenzophenanthrene (hexanitrile hexaazatriphenylene) was coated withAnd performing thermal vacuum evaporation to form a hole injection layer. On the hole injection layer, HT1 +.>After vacuum evaporation, HT2 is then deposited on the hole transport layerAfter formation as the first hole-regulating layer, the compound 1-1 synthesized in production example 1 was formed on the first hole-regulating layer at a film thickness +.>Vacuum evaporation is performed to form a second hole adjusting layer. As the light-emitting layer, the host compound 2-1 and the dopant BD1 compound (25:1, weight ratio) synthesized in production example 2 were combined in +.>Vacuum evaporation was performed on the thickness of (c). Then, ET 1->After formation as electronic regulating layer ET2 +.>And LiQ was vapor deposited at a weight ratio of 2:1, and thermal vacuum vapor deposition was sequentially performed as an electron transport layer. On the electron transport layer, lithium fluoride (LiF) is added in sequence +.>Thickness of aluminum->The thickness was evaporated to form a cathode, thereby manufacturing an organic light emitting device.
In the above process, the vapor deposition rate of the organic matter is maintainedLithium fluoride is maintained->Is kept at>Is a vapor deposition rate of (a).
With respect to examples 53 to 91 and comparative examples 7 to 13, experiments were conducted on organic light emitting devices manufactured using the respective compounds synthesized in manufacturing examples 1 and 2 as the first and second hole adjusting layers and the host material, and the results thereof, i.e., examples 53 to 91 and comparative examples 7 to 13, are shown in tables 4 to 6 below.
TABLE 4
TABLE 5
TABLE 6
The organic electroluminescent device using the combination of the compound derivatives of the chemical formula according to the present invention can regulate hole-adjusting and hole-injecting effects into a host, and the device according to the present invention exhibits excellent characteristics in terms of efficiency, driving voltage, stability by balancing holes and electrons of the organic luminescent device based on the chemical structure.

Claims (8)

1. An organic light emitting device, comprising: a first electrode, a second electrode disposed opposite to the first electrode, and a hole transport layer, a hole adjustment layer, and a light-emitting layer disposed between the first electrode and the second electrode,
the hole regulating layer contains a compound represented by the following chemical formula 1,
the hole regulating layer is disposed between the hole transporting layer and the light emitting layer, and
the light emitting layer includes a compound represented by the following chemical formula 2 or the following chemical formula 3:
Chemical formula 1
In the chemical formula 1, the chemical formula is shown in the drawing,
l1 to L3 are each independently a direct bond, or a substituted or unsubstituted arylene group,
ar3 is hydrogen, deuterium, or a substituted or unsubstituted aryl group,
ar1 and Ar2 are each independently hydrogen, deuterium, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted phenanthryl group, or a substituted or unsubstituted triphenylene group,
r1 and R2 are each independently hydrogen, deuterium, a halogen group, cyano, nitro, substituted or unsubstituted alkyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted haloalkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted aryl, or substituted or unsubstituted heterocyclyl,
a and b are each independently integers from 0 to 4,
a and b are each independently 2 or more, the substituents in parentheses are the same or different from each other,
chemical formula 2
In the chemical formula 2, the chemical formula is shown in the drawing,
l4 and L5 are each independently a direct bond, or a substituted or unsubstituted arylene group,
ar4 and Ar5 are each independently a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group,
Wherein at least one or more of Ar4 and Ar5 is a substituted or unsubstituted aryl group having 10 to 60 carbon atoms,
r3 and R4 are each independently hydrogen, deuterium, a halogen group, cyano, nitro, substituted or unsubstituted alkyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted haloalkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted aryl, or substituted or unsubstituted heterocyclyl,
c and d are each independently integers from 0 to 4,
c and d are each independently 2 or more, the substituents in parentheses are the same or different from each other,
chemical formula 3
In the chemical formula 3, the chemical formula is shown in the drawing,
l6 to L8 are each independently a direct bond, or a substituted or unsubstituted arylene group,
ar6 through Ar8 are each independently hydrogen, deuterium, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group,
r5 and R6 are each independently hydrogen, deuterium, a halogen group, cyano, nitro, substituted or unsubstituted alkyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted haloalkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted aryl, or substituted or unsubstituted heterocyclyl,
e and f are each independently integers from 0 to 4,
e and f are each independently 2 or more, the substituents in parentheses are the same or different from each other.
2. The organic light-emitting device according to claim 1, wherein Ar3 is hydrogen, deuterium, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthryl, or substituted or unsubstituted triphenylene.
3. The organic light emitting device of claim 1, wherein the formula 1 is selected from the following formulas:
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4. the organic light emitting device of claim 1, wherein the formula 2 is selected from the following formulas:
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5. the organic light emitting device of claim 1, wherein the formula 3 is selected from the following formulas:
6. an organic light-emitting device according to claim 1 wherein the hole-regulating layer consists of 1 to 3 layers.
7. The organic light-emitting device according to claim 1, wherein the hole-adjusting layer comprises 2 or more layers of hole-adjusting layers, and
at least one of the hole-regulating layers of 2 or more layers is provided in contact with the light-emitting layer.
8. The organic light-emitting device of claim 1, wherein the light-emitting layer is a blue light-emitting layer.
CN201980005002.0A 2018-02-28 2019-02-28 organic light emitting diode Active CN111213251B (en)

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