CN111116505B - Amine compound and organic light-emitting device thereof - Google Patents
Amine compound and organic light-emitting device thereof Download PDFInfo
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- C07D277/62—Benzothiazoles
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- 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
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Abstract
The invention relates to the technical field of organic electroluminescence, and provides an amine compound and an organic light-emitting device thereof. The amine compound is connected with three amino groups on the phenyl and is connected with substituent benzoxazolyl, benzothiazolyl or benzimidazolyl, and the compound is more stable due to the specific structure, so that the prepared organic light-emitting device has good thermal stability. In addition, the amine compound has higher refractive index, is used as a covering layer material, effectively solves the problem of total emission of an interface between an ITO film and a glass substrate and an interface between the glass substrate and air, reduces the total emission loss and waveguide loss in an OLED device, and improves the light extraction efficiency, thereby improving the luminous efficiency of an organic light-emitting device.
Description
Technical Field
The invention relates to the technical field of organic electroluminescence, in particular to an amine compound and an organic light-emitting device thereof.
Background
The Organic Light-Emitting Diode (OLED) has the advantages of self-luminescence, wide viewing angle, high contrast, low power consumption, high reaction rate, full color, simple manufacturing process, and the like, and the types of OLED displays can be monochrome, multi-color, full color, and the like. The OLED display can be divided into a Passive Matrix (PMOLED) display and an Active Matrix (AMOLED) display according to different driving methods. Depending on the materials used, the materials are simply divided into OLED (organic light-emitting diodes) and PLED (polymer light-emitting diodes), and mature products have been developed. The main advantage of PLEDs over OLEDs is their flexible large area display. However, due to the product lifetime problem, the OLED is still the main application of the current products on the market.
The light efficiency of the organic light emitting device is generally divided into internal light emitting efficiency and external light emitting efficiency. The internal light emission efficiency relates to how excitons are efficiently generated in organic layers such as a hole transport layer, a light emitting layer, and an electron transport layer disposed between a first electrode and a second electrode (i.e., between an anode and a cathode), and light conversion is achieved. Meanwhile, the external light emission efficiency (also referred to as "light coupling efficiency") means the efficiency of light generated in the organic layer, extracted outside the organic light emitting device, and the overall light efficiency of the organic light emitting device is low when the external light emission efficiency is low, even when high light conversion efficiency is obtained in the organic layer (that is, even when the internal light emission efficiency is high).
Recently, organic light emitting devices using a metal having a large work function in an anode having a top emission structure from the top are being used, and in light emitting devices having a top emission structure, semi-transparent electrodes such as LiF/Al/Ag, ca/Mg, and LiF/MgAg are used in a cathode. When light emitted to the light emitting layer enters other layers in such an organic light emitting device, only a part of the emitted light may be used because the light is totally reflected at an interface between the light emitting layer and the other layers when the light enters at a certain angle or more.
Therefore, in order to improve the light coupling efficiency, an organic light emitting device has been proposed in which a capping layer having a high refractive index is mounted on the outside of a translucent electrode having a low refractive index, and as a material of the capping layer, a material having a high refractive index and having excellent film stability or durability is required.
In general, in the future, the direction of OLEDs is to develop white light devices and full color display devices with high efficiency, long lifetime and low cost, but the industrialization of the technology still faces many key problems, such as the problem of the reduction of light emitting efficiency caused by total reflection loss and waveguide loss, and how to design materials with better performance for adjustment, which is always a problem that needs to be solved by those skilled in the art.
Disclosure of Invention
The invention aims to provide an amine compound and an organic light-emitting device thereof, the amine compound provided by the invention has good thermal stability and film-forming property, the synthetic method is simple and easy to operate, and the organic light-emitting device prepared by using the amine compound as a covering layer material has good light-emitting efficiency.
The present invention solves the above problems by providing an amine compound as a main component of a coating layer in an organic light-emitting device.
The amine compound is represented by a formula I,
wherein Ar is 1 Selected from formula II:
x is selected from O, S, NR 0 Wherein R is 0 One selected from phenyl, naphthyl, biphenyl and tolyl;
R 1 、R 2 、R 3 、R 4 one selected from the group consisting of H, methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, phenyl, biphenyl, terphenyl, naphthyl, acridinyl, phenanthryl, triphenylene, phenoxazinyl, phenothiazinyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, 9-phenylcarbazolyl, dibenzothienyl, dibenzofuranyl;
L 0 one selected from substituted or unsubstituted phenylene and substituted or unsubstituted naphthylene, wherein the substituent is one or more of methyl, ethyl, isopropyl, tertiary butyl and phenyl;
wherein Ar is 2 、Ar 3 、Ar 4 、Ar 5 、Ar 6 Independently selected from one of substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C3-C30 heteroaryl, ar 1 、Ar 2 、Ar 3 、Ar 4 、Ar 5 、 Ar 6 May be the same or different;
L 1 、L 2 、L 3 one selected from single bond, phenylene, biphenylene, naphthylene and anthrylene;
r is selected from one of hydrogen, substituted or unsubstituted C1-C10 alkyl and substituted or unsubstituted C6-C30 aryl;
n is selected from one of 0,1, 2 and 3.
The invention also provides an organic light-emitting device comprising a cathode, an anode and one or more organic layers, wherein at least one layer, preferably a covering layer, of the organic layers contains any one or a combination of at least two of the amine compounds.
Advantageous effects
The invention has the beneficial effects that:
the invention provides an amine compound and an organic light-emitting device thereof, on one hand, three amino groups are connected on a phenyl group, and substituent groups such as benzoxazolyl, benzothiazolyl or benzimidazolyl are connected, so that benzene ring structures of benzoxazole, benzothiazole and benzimidazole have high plasticity in the aspect of chemical modification due to pi-pi stacking and the existence of interaction between pi cations on an aromatic conjugate plane of five-membered nitrogen-containing heterocyclic groups such as benzoxazole, benzothiazole and benzimidazole. Benzoxazole, benzothiazole and benzimidazole as substituents can effectively inhibit aggregation-induced fluorescence quenching caused by plane conjugation, and increase the luminous efficiency of the luminescent material, and the thermal stability and solubility of molecules.
On the other hand, different substituents such as alkyl, aryl and heteroaryl are introduced to different positions of the amino group, so that the symmetry of the whole molecule can be reduced, the number of molecular isomers is increased, the film forming property of the molecule is better, and the thermal stability of the film is improved.
In addition, the amine compound has higher refractive index, effectively solves the problem of total emission of the interface of the ITO film and the glass substrate and the interface of the glass substrate and the air, reduces the total emission loss and waveguide loss in the OLED device, and improves the light extraction efficiency, thereby improving the luminous efficiency of the organic light-emitting device.
The amine compound provided by the invention is applied to an organic light-emitting device and can be used as a covering layer material, and the organic light-emitting device prepared by the amine compound has the advantage of good luminous efficiency.
Drawings
FIG. 1 is a drawing showing Compound 1 of the present invention 1 H NMR chart;
FIG. 2 is a drawing of Compound 24 of the present invention 1 H NMR chart;
FIG. 3 is a drawing showing a scheme for preparing compound 29 of the present invention 1 H NMR chart;
FIG. 4 is a drawing showing a scheme for preparing compound 35 of the present invention 1 H NMR chart;
FIG. 5 shows Compound 43 of the present invention 1 H NMR chart;
FIG. 6 shows Compound 62 of the present invention 1 H NMR chart;
FIG. 7 shows Compound 119 of the present invention 1 H NMR chart;
FIG. 8 is a drawing of Compound 126 of the present invention 1 H NMR chart;
FIG. 9 shows a scheme for preparing compound 129 of the present invention 1 H NMR chart.
Detailed Description
The following will clearly and completely describe the technical solutions of the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
The alkyl refers to a hydrocarbyl formed by subtracting one hydrogen atom from an alkane molecule, and can be straight-chain alkyl, branched-chain alkyl or cycloalkyl. The straight chain alkyl group includes, but is not limited to, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, undecyl, dodecyl, and the like; the branched alkyl group includes, but is not limited to, an isomeric group of isopropyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, an isomeric group of n-hexyl, an isomeric group of n-heptyl, an isomeric group of n-octyl, an isomeric group of n-nonyl, an isomeric group of n-decyl, etc.; the cycloalkyl group includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc., but is not limited thereto. The above alkyl group is preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group and a tert-butyl group.
The chain alkyl group having more than two carbon atoms such as propyl, butyl, pentyl and the like described in the present invention includes isomers thereof such as isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl and the like, but is not limited thereto.
The aryl group in the present invention refers to a general term of monovalent group remaining after one hydrogen atom is removed from an aromatic nucleus carbon of an aromatic hydrocarbon molecule, and may be monocyclic aryl group, polycyclic aryl group or condensed ring aryl group, and examples may include phenyl group, biphenyl group, terphenyl group, naphthyl group, binaphthyl group, anthracenyl group, phenanthrenyl group, triphenylenyl group, pyrenyl group, fluorenyl group, spirobifluorenyl group, chrysenyl group, fluoranthenyl group, benzofluorenyl group, naphthofluorenyl group, benzofluoranthenyl group and the like, but are not limited thereto.
The heteroaryl group according to the present invention is a general term in which a hydrogen atom is removed from a nuclear carbon of an aromatic heterocyclic ring composed of carbon and a hetero atom including, but not limited to, oxygen, sulfur and nitrogen atoms, leaving a monovalent group, and may be a monocyclic heteroaryl group, a polycyclic heteroaryl group or a fused ring heteroaryl group, and examples may include carbazolyl, furyl, thienyl, pyrrolyl, imidazolyl, oxazolyl, thiazolyl, pyridyl, pyrimidinyl, triazinyl, acridinyl, phenazinyl, benzofuryl, benzothienyl, dibenzofuryl, dibenzothienyl, benzocarbazolyl, benzoxazolyl, benzothiazolyl, benzimidazolyl, phenoxazinyl, phenothiazinyl, phenoxathiin, quinazolinyl, quinoxalinyl, quinolyl, isoquinolyl, purinyl, indolyl, azacarbazolyl, azafluorenyl, azaspirobifluorenyl, xanthenyl, thiaanthracenyl and the like, but not limited thereto.
The term "C6 to C30" in the "substituted or unsubstituted C6 to C30 aryl group" as used herein means the number of carbon atoms contained in the unsubstituted aryl group, not including the number of carbon atoms of the substituent; the term "C3 to C30" in the "substituted or unsubstituted C3 to C30 heteroaryl group" means the number of carbon atoms contained in the unsubstituted heteroaryl group, and the number of carbon atoms of the substituent is not included. And so on.
The "substituted or unsubstituted" in the present invention means that the group is unsubstituted or mono-or polysubstituted by a group independently selected from, but not limited to, deuteroyl, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C2-C15 heteroaryl, substituted or unsubstituted amine, and the like, preferably by a group selected from, but not limited to deuteroyl, methyl, ethyl, isopropyl, tert-butyl, phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, benzophenanthryl, perylenyl, pyrenyl, benzyl, fluorenyl, 9-dimethylfluorenyl, dianilino, dimethylamino, carbazolyl, 9-phenylcarbazolyl, acridinyl, furanyl, thienyl, benzofuranyl, benzothiophenyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, dibenzofuranyl, dibenzothienyl, phenothiazinyl, phenoxazinyl, indolyl, and the like.
The invention provides an amine compound, which is represented by a general formula I,
wherein Ar is 1 Selected from formula II:
x is selected from O, S, NR 0 Wherein R is 0 One selected from phenyl, naphthyl, biphenyl and tolyl;
R 1 、R 2 、R 3 、R 4 selected from the group consisting of H, methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, phenyl, biphenyl, terphenyl, naphthyl, acridinyl, phenanthryl, triphenylene, phenoxazinyl, phenothiazinyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, 9-benzeneOne of carbazolyl, dibenzothienyl and dibenzofuranyl;
L 0 one selected from substituted or unsubstituted phenylene and substituted or unsubstituted naphthylene, wherein the substituent is one or more of methyl, ethyl, isopropyl, tertiary butyl and phenyl;
wherein Ar is 2 、Ar 3 、Ar 4 、Ar 5 、Ar 6 Independently selected from one of substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C3-C30 heteroaryl, ar 1 、Ar 2 、Ar 3 、Ar 4 、Ar 5 、 Ar 6 May be the same or different;
L 1 、L 2 、L 3 one selected from single bond, phenylene, biphenylene, naphthylene and anthrylene;
r is selected from one of hydrogen, substituted or unsubstituted C1-C10 alkyl and substituted or unsubstituted C6-C30 aryl;
n is selected from one of 0,1, 2 and 3.
Preferably, formula I is selected from one of the groups represented by formulae I-a to I-f:
preferably, formula II is selected from one of the groups represented by formulas II-a to II-d below:
preferably, L 0 One selected from the group consisting of the following formulas V-1 to V-10:
preferably, ar is 2 、Ar 3 、Ar 4 、Ar 5 、Ar 6 Independently selected from one of the following groups:
preferably, the amine compound is selected from one of the following chemical structures:
the amine compound shown in the formula I is obtained through the following synthetic route:
case 1: l is a radical of an alcohol 1 、L 2 、L 3 When the bond is a single bond:
Step1:
the intermediate C, the intermediate D and the intermediate D are synthesized by the same method,
Step2:
Case 2: l is 1 、L 2 、L 3 When not a single bond:
Step1:
Step2:
the intermediate C and the intermediate D are synthesized by the same method
Step3:
Case 3: l is a radical of an alcohol 1 、L 2 、L 3 When not all are single bonds:
using the corresponding intermediate (A/B) , C. Reaction of/C, D,/D) with a trihalobenzene compound.
The intermediate product and the amine compound shown in the chemical formula I can be obtained through a Buchwald reaction and a Suzuki coupling reaction. Wherein, X is Cl, br or I.
The source of the raw materials used in the above-mentioned reactions is not particularly limited, and the amine compound of the present invention can be obtained by using commercially available raw materials or by a preparation method known to those skilled in the art. The present invention has no special limitation on the above reaction, and the preparation method is simple and easy to operate by adopting the conventional reaction well known by the technical personnel in the field.
The invention also provides an organic light-emitting device which comprises a cathode, an anode and one or more organic layers, wherein the organic layers comprise one or more organic layers arranged between the two electrodes and outside the two electrodes, and the organic layers comprise at least one of a hole injection layer, a hole transmission layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transmission layer, an electron injection layer and a covering layer; the organic layer contains any one or a combination of at least two of the amine compounds.
Preferably, the organic layer of the present invention includes a covering layer, and the covering layer contains any one or a combination of at least two of the amine compounds of the present invention.
Preferably, the cover layer is located on a side of the cathode facing away from the anode.
The light emitting device of the present invention is generally formed on a substrate. The substrate may be any substrate as long as it does not change when forming electrodes or organic layers, for example, a substrate of glass, plastic, polymer film, silicon, or the like. When the substrate is opaque, the electrode opposite thereto is preferably transparent or translucent.
In the light-emitting device of the present invention, at least one of the anode and the cathode is transparent or translucent, and preferably, the cathode is transparent or translucent.
As the anode material, a conductive metal oxide film, a translucent metal thin film, or the like is generally used. Examples of the method for producing the film include a film (NESA or the like) made of a conductive inorganic compound containing indium oxide, zinc oxide, tin oxide, and a composite thereof, such as indium tin oxide (abbreviated as ITO) or indium zinc oxide (abbreviated as IZO), and a method using gold, platinum, silver, copper, or the like. As the anode, an organic transparent conductive film such as polyaniline or a derivative thereof, polythiophene or a derivative thereof, or the like can be used. The anode may have a laminate structure of 2 or more layers, and preferably, the anode of the present invention is an opaque ITO-Ag-ITO substrate.
The hole injection layer is to improve the efficiency of hole injection from the anode into the hole transport layer and the light emitting layer. The hole injection material of the present invention may be a metal oxide such as molybdenum oxide, silver oxide, vanadium oxide, tungsten oxide, ruthenium oxide, nickel oxide, copper oxide, titanium oxide, or a low molecular weight organic compound such as phthalocyanine-based compound or polycyano-group-containing conjugated organic material, but is not limited thereto. Preferably, the hole injection layer of the present invention is selected from 4,4',4 ″ -tris [ 2-naphthylphenylamino ] triphenylamine (abbreviation: 2T-NATA), 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene (abbreviation: HAT-CN), 4',4 ″ -tris (N, N-diphenylamino) triphenylamine (abbreviated as TDATA), 4',4 ″ -tris [ N- (3-methylphenyl) -N-phenylamino ] triphenylamine (abbreviated as MTDATA), copper (II) phthalocyanine (abbreviated as CuPc), N' -bis [4- [ bis (3-methylphenyl) amino ] phenyl ] -N, N '-diphenyl-biphenyl-4, 4' -diamine (abbreviated as DNTPD), N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine (abbreviated as NPB), and the like, which may be a single structure composed of a single substance, or a single-layer structure or a multi-layer structure formed of different substances.
The hole transport layer is a layer having a function of transporting holes. The hole transport material of the present invention is preferably a material having a good hole transport property, and may be selected from small molecular materials such as aromatic amine derivatives, carbazole derivatives, stilbene derivatives, triphenyldiamine derivatives, styrene compounds, butadiene compounds, and polymer materials such as poly-p-phenylene derivatives, polyaniline and derivatives thereof, polythiophene and derivatives thereof, polyvinylcarbazole and derivatives thereof, polysilane and derivatives thereof, but is not limited thereto. <xnotran> , N, N ' - -N, N ' - (1- ) -1,1' - -4,4' - (: NPB), N, N ' - ( -1- ) -N, N ' - () -2,2' - (: α -NPD), N, N ' - -N, N ' - (3- ) -1,1' - -4,4' - (: TPD), 4,4' - [ N, N- (4- ) ] (: TAPC), 4,4',4"- ( -9- ) (: TCTA), 2,2,7,7- ( ) -9,9- (: spiro-TAD) , , . </xnotran>
The electron blocking layer is a layer which transports holes and blocks electrons, and is preferably selected from N, N ' -bis (naphthalene-1-yl) -N, N ' -bis (phenyl) -2,2' -dimethylbenzidine (abbreviated as α -NPD), 4',4 ″ -tris (N, N-diphenylamino) triphenylamine (abbreviated as TDATA), N ' -diphenyl-N, N ' -bis (3-methylphenyl) -1,1' -biphenyl-4, 4' -diamine (abbreviated as TPD), 4' -cyclohexylbis [ N, N-bis (4-methylphenyl) aniline ] (abbreviated as TAPC), 2, 7-tetrakis (diphenylamino) -9, 9-spirobifluorene (abbreviated as Spiro-TAD), and the like, and may have a single structure composed of a single substance or a single-layer structure or a multilayer structure composed of different substances.
The light-emitting layer is a layer having a light-emitting function. The light-emitting layer material includes a light-emitting layer host material AND a light-emitting layer guest material, AND preferably, the host material of the present invention is selected from 4,4' -bis (9-carbazole) biphenyl (abbreviated as CBP), 9, 10-bis (2-naphthyl) anthracene (abbreviated as ADN), 4-bis (9-carbazolyl) biphenyl (abbreviated as CPB), 9' - (1, 3-phenyl) bis-9H-carbazole (abbreviated as mCP), 4',4 ″ -tris (carbazol-9-yl) triphenylamine (abbreviated as TCTA), 9, 10-bis (1-naphthyl) anthracene (abbreviated as α -AND), N ' -bis- (1-naphthyl) -N, N ' -diphenyl- [1,1':4',1 ″,4 ″,1' ″ -tetrabiphenyl ] -4,4' ″ -diamino (abbreviated as 4P-NPB), 1,3, 5-tris (9-carbazolyl) benzene (abbreviated as TCP), AND the like, AND the light-emitting layer material may be a single layer structure, or a multilayer structure formed of different substances.
The guest material of the light-emitting layer of the present invention may include one or a mixture of two or more materials, and the light-emitting material is classified into a blue light-emitting material, a green light-emitting material, and a red light-emitting material. Preferably, the light-emitting material of the present invention is a green light-emitting material, and the green light-emitting layer guest is selected from tris (8-hydroxyquinoline) aluminum (III) (Alq for short) 3 ) Tris (2-phenylpyridine) -iridium (Ir (ppy) for short) 3 ) Bis (2-phenylpyridine) iridium acetylacetonate (abbreviated as Ir (ppy) 2 (acac)), tris [2- (p-tolyl) pyridine-C2, N]Iridium (III) (abbreviation: ir (mppy) 3 ) Tris [2- (3-methyl-2-pyridyl) phenyl group]Iridium (Industred: ir (3 mppy) 3 ) Bis [2- (2-benzothiazolyl) phenol]Zinc (abbreviation: zn (BTZ) 2 ) And so on.
The doping ratio of the host material and the guest material of the light-emitting layer is preferably varied depending on the materials used, and the doping film thickness ratio of the guest material of the light-emitting layer is usually 0.01 to 20%, preferably 0.1 to 15%, more preferably 1 to 10%.
The hole-blocking layer is a layer which transports electrons and blocks holes, and is preferably a layer according to the present inventionThe hole blocking layer is selected from 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline (BCP), 1,3, 5-tri (N-phenyl-2-benzimidazole) benzene (TPBi), and tri (8-hydroxyquinoline) aluminum (III) (Alq) 3 ) 8-hydroxyquinoline-lithium (Liq), bis (2-methyl-8-hydroxyquinoline) (4-phenylphenol) aluminum (III) (BALq), 3- (biphenyl-4-yl) -5- (4-tert-butylphenyl) -4-phenyl-4H-1, 2, 4-Triazole (TAZ), and the like, which may be a single structure composed of a single substance or a single-layer structure or a multi-layer structure composed of different substances.
The electron transport layer is a layer having a function of transporting electrons. The electron transport material of the present invention can be selected from known metal complexes of oxadiazole derivatives, anthraquinone dimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, tetracyanoanthraquinone dimethane and its derivatives, fluorenone derivatives, diphenoquinone derivatives, 8-hydroxyquinoline and its derivatives, and preferably, the electron transport layer is selected from 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline (BCP), 1,3, 5-tris (N-phenyl-2-benzimidazole) benzene (TPBi), and tris (8-hydroxyquinoline) aluminum (III) (Alq) 3 ) 8-hydroxyquinoline-lithium (Liq), bis (2-methyl-8-hydroxyquinoline) (4-phenylphenol) aluminum (III) (BALq), and 3- (biphenyl-4-yl) -5- (4-t-butylphenyl) -4-phenyl-4H-1, 2, 4-Triazole (TAZ), and the like, and they may be a single structure composed of a single substance or a single-layer structure or a multi-layer structure composed of different substances.
The electron injection layer is to improve the efficiency of electron injection from the cathode into the electron transport layer and the light emitting layer. The electron injection material of the present invention may Be Li, na, K, rb, cs, be, mg, ca, sr, ba, lithium fluoride, sodium fluoride, potassium fluoride, rubidium fluoride, cesium fluoride, magnesium fluoride, calcium fluoride, lithium oxide, cesium carbonate, lithium acetate, sodium acetate, potassium acetate, lithium tetrakis (8-quinolinolato) boron, lithium 8-quinolinolato, or the like, and may Be a single structure composed of a single substance, or a single-layer structure or a multi-layer structure composed of different substances. Preferably, the electron injection layer according to the present invention may be selected from LiF.
As the cathode material, a metal material having a small work function is generally preferable. For example, metals such as lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, ytterbium, and the like, alloys of 2 or more of these metals, or alloys of 1 or more of these metals and 1 or more of gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, tin, graphite, or graphite intercalation compounds, and the like can be used. Examples of the alloy include magnesium-silver alloy, magnesium-indium alloy, magnesium-aluminum alloy, indium-silver alloy, lithium-aluminum alloy, lithium-magnesium alloy, lithium-indium alloy, and calcium-aluminum alloy. The cathode may have a laminate structure of 2 or more layers. Preferably, the cathode of the invention uses Ag or Mg-Ag alloy or thin Al.
Preferably, the coating layer of the present invention is selected from any one or a combination of at least two of the amine compounds of the present invention or from Alq 3 。
The film thicknesses of the hole transporting layer and the electron transporting layer may be selected as appropriate depending on the materials used, and may be selected so as to achieve appropriate values of the driving voltage and the light emission efficiency. Therefore, the film thicknesses of the hole transporting layer and the electron transporting layer are, for example, 1nm to 1um, preferably 2nm to 500nm, and more preferably 5nm to 200nm.
The order and number of layers to be laminated and the thickness of each layer may be appropriately selected in consideration of the light emission efficiency and the lifetime of the device.
The structure of the amine compound and the organic light-emitting device thereof is preferably as follows: substrate/anode/hole injection layer/hole transport layer/light emitting layer/electron transport layer/electron injection layer/cathode. However, the structure of the organic light emitting device is not limited thereto. The amine compound and the organic light-emitting device thereof can be selected and combined according to the parameter requirements of the device and the characteristics of materials, and part of organic layers can be added or omitted.
The method for forming each layer in the organic light-emitting device is not particularly limited, and any one of vacuum evaporation, spin coating, vapor deposition, blade coating, laser thermal transfer, electrospray, slit coating, and dip coating may be used, and in the present invention, vacuum evaporation is preferably used.
The organic light-emitting device can be widely applied to the fields of panel display, lighting sources, flexible OLEDs, electronic paper, organic solar cells, organic photoreceptors or organic thin film transistors, signs, signal lamps and the like.
The invention is explained in more detail by the following examples, without wishing to restrict the invention accordingly. Based on this description, one of ordinary skill in the art will be able to practice the invention and prepare other compounds and devices according to the invention within the full scope of the disclosure without undue inventive effort.
Preparation and characterization of the Compounds
Description of raw materials, reagents and characterization equipment:
the raw materials used in the following examples are not particularly limited, and may be commercially available products or prepared by methods known to those skilled in the art.
Mass spectrometry an AXIMA-CFR plus matrix-assisted laser desorption ionization flight mass spectrometer from Kratos Analytical, inc. of Kratos Analytical, isuzin, inc. was used, chloroform was used as the solvent;
the element analysis uses a Vario EL cube type organic element analyzer of Elementar company in Germany, and the sample mass is 5-10 mg;
nuclear magnetic resonance ( 1 H NMR Spectroscopy) A nuclear magnetic resonance spectrometer model Bruker-510 (Bruker, germany), 400MHz, CDCl 3 As solvent, TMS as internal standard.
[ Synthesis example 1] Synthesis of Compound 1
Synthesis of intermediate 1-1
Toluene (600 mL), 4- (2-benzoxazolyl) aniline (44.15 g,0.21 mol), 1-bromobenzene (32.97g, 0.21mol), palladium acetate (0.61g, 0.0027mol), sodium tert-butoxide (33.7 g,0.351 mol) and tri-tert-butylphosphine (10.8 mL of a 1.0M solution in toluene, 0.0108 mol) were added sequentially to a 1L reaction flask under nitrogen blanket and reacted for 2 hours under reflux. After the reaction is stopped, the mixture is cooled to room temperature, filtered by using kieselguhr, the filtrate is concentrated, recrystallized by using methanol, filtered by suction and rinsed by using methanol to obtain a recrystallized solid, and the intermediate 1-1 (53.51 g, the yield is about 81%) is obtained, and the purity of the solid is not less than 98.4% by HPLC (high performance liquid chromatography).
Synthesis of intermediate 2-1
Toluene (600 mL), intermediate 1-1 (42.94g, 0.15mol), c-1 (54.27g, 0.15mol), palladium acetate (0.61g, 0.0027mol), sodium tert-butoxide (33.7g, 0.351mol), and tri-tert-butylphosphine (10.8 mL of a 1.0M solution in toluene, 0.0108 mol) were added to a 1L reaction flask in this order under nitrogen. And reacted under reflux for 2 hours. After the reaction is stopped, the mixture is cooled to room temperature, filtered by using kieselguhr, the filtrate is concentrated, recrystallized by using methanol, filtered by suction and rinsed by using methanol to obtain a recrystallized solid, and the intermediate 2-1 (59.30 g, the yield is about 76%) is obtained, and the purity of the solid is not less than 98.7% by HPLC (high performance liquid chromatography).
Synthesis of Compound 1
Under the protection of nitrogen, a toluene solvent (450 ml), d-1 (12.18g, 72mmol), intermediate 2-1 (18.73g, 36mmol), pd were sequentially added to a 1L reaction flask 2 (dba) 3 (990mg, 1.08mmol), BINAP (1.65g, 16.5mmol) and sodium tert-butoxide (9.9g, 100.8mmol) were dissolved with stirring, and the reaction mixture was refluxed for 24 hours under a nitrogen atmosphere, and after completion of the reaction, the reaction mixture was washed with dichloromethane and distilled water, and subjected to separation extraction. The organic layer was dried over anhydrous magnesium sulfate, filtered, and the solvent was removed, and the residue was washed with cyclohexane: ethyl acetate =10, and the solid compound 1 is finally obtained by column chromatography purification and purification using the eluent ethyl acetate =1 (19.30 g, yield 77%), and the purity of the solid is ≧ 99.2% by HPLC.
Mass spectrum m/z:696.30 (calculated: 696.29). Theoretical element content (%) C 49 H 36 N 4 O: c,84.46; h,5.21; n,8.04; o,2.30 measured elemental content (%): c,84.47; h,5.20; n,8.03; o,2.31. 1 H NMR(400MHz,CDCl 3 ) (δ, ppm): 7.84-7.78 (m, 2H), 7.64 (dd, 2H), 7.42-7.35 (m, 4H), 7.24 (t, 10H), 7.11-7.05 (m, 10H), 7.02-6.97 (m, 5H), 6.62 (s, 1H), 6.61 (s, 1H), 6.60 (s, 1H). The above results confirmed that the obtained product was the objective product.
Synthesis example 2 Synthesis of Compound 24
The same procedure was repeated except for changing 1-bromobenzene in Synthesis example 1 to equimolar 1-bromotriphenylene to give compound 24 (24.07 g, yield about 79%) having a solid purity ≧ 98.9% by HPLC.
Mass spectrum m/z:846.39 (calculated: 846.34). Theoretical element content (%) C 61 H 42 N 4 O: c,86.50; h, 5.00; n,6.61; o,1.89 measured element content (%): c,86.49; h,5.01; n,6.63; o,1.87. 1 H NMR(600MHz,CDCl 3 ) (δ, ppm): 8.95 (d, 1H), 8.52-8.48 (m, 2H), 8.46 (d, 1H), 8.33 (dd, 2H), 8.27 (dd, 1H), 7.77 (dd, 1H), 7.73-7.67 (m, 2H), 7.67-7.60 (m, 6H), 7.52 (dd, 1H), 7.38 (dd, 2H), 7.24 (t, 8H), 7.13-7.05 (m, 8H), 7.02 (t, 1H), 7.00 (t, 2H), 6.98 (t, 1H), 6.00 (s, 1H), 5.60 (s, 1H), 5.50 (s, 1H). The above results confirmed that the obtained product was the objective product.
Synthesis example 3 Synthesis of Compound 29
The same procedures were repeated except for changing 1-bromobenzene in synthesis example 1 to equimolar 3-bromopyridine to obtain compound 29 (20.33 g, yield: 81%) with a solid purity of 99.1% or more by HPLC.
Mass spectrum m/z:697.30 (calculated: 697.28). Theoretical element content (%) C 48 H 35 N 5 O: c,82.62; h, 5.06; n,10.04; o,2.29 measured element content (%): c,82.63; h,5.05; n,10.05; o,2.28. 1 H NMR(400MHz,CDCl 3 ) (δ, ppm): 8.44 (d, 1H), 8.29 (d, 1H), 8.08 (d, 1H), 7.79-7.75 (m, 1H), 7.61-7.56 (m, 1H), 7.47 (d, 1H), 7.38-7.34 (m, 2H), 7.28 (s, 2H), 7.21 (t, 9H), 7.11 (d, 3H), 7.07 (d, 6H), 6.96 (d, 4H), 6.57 (s, 1H), 6.43 (s, 2H). The above results confirmed that the obtained product was the objective product.
[ Synthesis example 4] Synthesis of Compound 35
The 1-bromobenzene in synthesis example 1 was replaced with equimolar 3-bromo-N-phenylcarbazole, and the other steps were repeated in the same manner to obtain compound 29 (24.83 g, yield about 80%) with a solid purity of 99.3% or more by HPLC.
Mass spectrum m/z:861.36 (calculated value: 861.35). Theoretical element content (%) C 61 H 43 N 5 O: c,84.99; h,5.03; n,8.12; o,1.86 measured elemental content (%): c,85.00; h,5.02; n,8.11; o,1.87. 1 H NMR(400MHz,CDCl 3 ) (δ, ppm): 8.31-8.28 (m, 1H), 8.00-7.95 (m, 2H), 7.93 (d, 1H), 7.88 (d, 1H), 7.86-7.81 (m, 2H), 7.79-7.75 (m, 1H), 7.64 (dd, 2H), 7.60 (t, 2H), 7.48-7.45 (m, 2H), 7.38 (dd, 2H), 7.32 (dt, 2H), 7.31-7.26 (m, 2H), 7.24 (t, 8H), 7.11-7.05 (m, 8H), 7.01-6.98 (m, 4H), 6.67 (s, 1H), 6.66 (s, 1H), 6.62 (s, 1H). The above results confirmed that the obtained product was the objective product.
Synthesis example 5 Synthesis of Compound 43
The same procedure was repeated except for changing d-1 to d-43 in Synthesis example 1 to give compound 43 (29.72 g, yield: 70%) having a purity of 99.1% by HPLC.
Mass spectrum m/z:848.39 (calcd: 848.35). Theoretical element content (%) C 61 H 44 N 4 O: c,86.29; h, 5.22; n,6.60; measured element of O,1.88Content (%): c,86.30; h,5.21; n,6.61; o,1.87. 1 H NMR(400MHz,CDCl 3 ) (δ, ppm): 8.09 (d, 2H), 7.82-7.76 (m, 1H), 7.62-7.57 (m, 1H), 7.50 (dd, 9H), 7.39 (t, 6H), 7.35-7.30 (m, 6H), 7.24 (dd, 6H), 7.19-7.15 (m, 8H), 7.02 (t, 2H), 6.63 (s, 1H), 6.57 (s, 1H), 6.56 (s, 1H). The above results confirmed that the obtained product was the objective product.
[ Synthesis example 6] Synthesis of Compound 62
Synthesis of intermediates 1 to 62
To a 1L reaction flask were added toluene (600 mL), 4- (2-benzothiazolyl) aniline (47.52 g,0.21 mol), 1-bromobenzene (32.97g, 0.21mol), palladium acetate (0.61g, 0.0027mol), sodium tert-butoxide (33.7 g,0.351 mol), and tri-tert-butylphosphine (10.8 mL of a 1.0M solution in toluene, 0.0108 mol) in that order under nitrogen. And reacted under reflux for 2 hours. After the reaction was stopped, the mixture was cooled to room temperature, filtered through celite, the filtrate was concentrated, recrystallized from methanol, filtered with suction and rinsed with methanol to give a recrystallized solid, intermediate 1-62 (49.53 g, yield about 78%), and purity ≧ 98.6% by HPLC.
Synthesis of intermediates 2 to 62
Toluene (600 mL), intermediates 1-62 (45.36g, 0.15mol), c-62 (47.60g, 0.15mol), palladium acetate (0.61g, 0.0027mol), sodium tert-butoxide (33.7g, 0.351mol), and tri-tert-butylphosphine (10.8 mL of a 1.0M solution in toluene, 0.0108 mol) were added to a 1L reaction flask in this order under nitrogen. And reacted under reflux for 2 hours. After the reaction is stopped, the mixture is cooled to room temperature, filtered by using kieselguhr, the filtrate is concentrated, recrystallized by using methanol, filtered by suction and rinsed by using methanol to obtain a recrystallized solid, and the intermediate 2-62 (51.64 g, the yield is about 70%) is obtained, and the purity of the solid is not less than 98.8% by HPLC (high performance liquid chromatography).
Synthesis of intermediates 3-62
Toluene (600 mL), intermediates 2-62 (49.18g, 0.10mol), d-62 (30.24g, 0.10mol), palladium acetate (0.41g, 0.0018mol), sodium tert-butoxide (22.6 g, 0.235mol), and tri-tert-butylphosphine (7.2 mL of a 1.0M solution in toluene, 0.0072 mol) were sequentially added to a 1L reaction flask under nitrogen protection. And reacted under reflux for 2 hours. After the reaction is stopped, the mixture is cooled to room temperature, filtered through celite, the filtrate is concentrated, recrystallized through methanol, filtered through suction and rinsed through methanol to obtain a recrystallized solid, and the intermediate 3-62 (53.67 g, the yield is about 68%) is obtained, and the purity of the solid is not less than 98.9% through HPLC (high performance liquid chromatography).
Synthesis of Compound 62
Under the protection of nitrogen, a 1L reaction flask was charged with toluene solvent (450 ml), e-62 (7.10 g, 36mmol), intermediate 3-62 (28.42g, 36mmol), pd 2 (dba) 3 (990mg, 1.08mmol), BINAP (1.65g, 16.5 mmol) and sodium tert-butoxide (9.9g, 100.8mmol) were dissolved with stirring, and the reaction mixture was refluxed for 24 hours under a nitrogen atmosphere, and after completion of the reaction, the reaction mixture was washed with dichloromethane and distilled water, and subjected to liquid separation and extraction. The organic layer was dried over anhydrous magnesium sulfate, filtered, and the solvent was removed, and the residue was washed with cyclohexane: ethyl acetate =10, and column chromatography purification and purification are performed as eluent to obtain the solid compound 62 (23.60 g, yield 69%) with purity ≧ 99.4% by HPLC.
Mass spectrum m/z:917.39 (calculated: 917.37). Theoretical element content (%) C 64 H 47 N 5 O 2 : c,83.73; h,5.16; n,7.63; o,3.49 measured elemental content (%): c,83.75; h,5.16; n,7.62; and O,3.48. 1 H NMR(400MHz,CDCl 3 ) (δ, ppm): 8.13-8.04 (m, 3H), 8.02 (dd, 1H), 7.77-7.72 (m, 2H), 7.72-7.67 (m, 2H), 7.56-7.60 (m, 4H), 7.50 (dd, 2H), 7.46 (d, 1H), 7.44 (dd, 4H), 7.41 (q, 2H), 7.39 (d, 3H), 7.35-7.31 (m, 1H), 7.24 (t, 2H), 7.19-7.13 (m, 4H), 7.08 (dd, 2H), 7.02-6.99 (m, 1H), 6.97-6.94 (m, 4H), 6.64 (s, 1H), 6.63 (s, 1H), 6.60 (s, 1H), 2.33 (s, 6H). The above results confirmed that the obtained product was the objective product.
[ Synthesis example 7] Synthesis of Compound 119
The same procedures were repeated except for changing 4- (2-benzoxazolyl) aniline of Synthesis example 1 to equimolar 4- (1-phenyl-1H-benzimidazol-2-yl) aniline and changing diphenylamine to equimolar N-phenyl-1-naphthylamine to obtain 119 (23.54 g, yield about 75%) as a compound having a purity of 99.5% by HPLC.
Mass spectrum m/z:871.39 (calculated: 871.37). Theoretical element content (%) C 63 H 45 N 5 : c,86.77; h,5.20; n,8.03 measured elemental content (%): c,86.78; h,5.20; and N,8.02. 1 H NMR(400MHz,CDCl 3 ) (δ, ppm): 8.50 (dd, 2H), 8.28-8.14 (m, 3H), 8.03-7.95 (m, 1H), 7.87 (dd, 2H), 7.72 (t, 1H), 7.67-7.63 (m, 3H), 7.62-7.55 (m, 2H), 7.55-7.51 (m, 3H), 7.49-7.39 (m, 8H), 7.38-7.28 (m, 2H), 7.27-7.15 (m, 10H), 7.08 (dd, 2H), 7.01 (t, 1H), 7.00 (t, 1H), 6.98 (t, 1H), 5.69 (s, 2H), 5.47 (s, 1H). The above results confirmed that the obtained product was the objective product.
Synthesis example 8 Synthesis of Compound 126
Under the protection of nitrogen, a toluene solvent (450 ml), c-126 (11.33g, 36mmol), intermediate 1-1 (30.92g, 108mmol), pd were added in sequence to a 1L reaction flask 2 (dba) 3 (990mg, 1.08mmol), BINAP (1.65g, 16.5mmol) and sodium tert-butoxide (9.9g, 100.8mmol) were dissolved with stirring, and the reaction mixture was refluxed for 24 hours under a nitrogen atmosphere, and after completion of the reaction, the reaction mixture was washed with dichloromethane and distilled water, and subjected to separation extraction. The organic layer was dried over anhydrous magnesium sulfate, filtered, and the solvent was removed, and the residue was washed with cyclohexane: ethyl acetate =10, and column chromatography purification and purification are performed as eluent to obtain the solid compound 126 (25.14 g, yield 75%) with purity ≧ 99.5% by HPLC.
Mass spectrum m/z:930.35 (calculated: 930.33). Theoretical element content (%) C 63 H 42 N 6 O 3 ：C，81.27；H, 4.55; n,9.03; o,5.16 measured elemental content (%): c,81.28; h,4.54; n,9.01; and O,5.18. 1 H NMR(400MHz,CDCl 3 ) (δ, ppm): 8.11 (d, 6H), 7.79-7.75 (m, 3H), 7.58-7.53 (m, 3H), 7.39-7.33 (m, 12H), 7.20 (d, 6H), 7.17-7.13 (m, 9H), 6.67 (s, 3H). The above results confirmed that the obtained product was the objective product.
Synthesis example 9 Synthesis of Compound 129
The same procedure was repeated except for changing c-1 to c-129 in Synthesis example 1 to give 129 (23.98 g, yield: 72%) as a compound having a purity of 99.6% by HPLC.
Mass spectrum m/z:924.39 (calculated: 924.38). Theoretical element content (%) C 67 H 48 N 4 O: c,86.98; h,5.23; n,6.06; o,1.73 measured elemental content (%): c,86.99; h,5.23; n,6.05; o,1.73. 1 H NMR(400MHz,CDCl 3 ) (δ, ppm): 7.91 (d, 2H), 7.64 (dd, 2H), 7.45 (d, 2H), 7.40-7.34 (m, 4H), 7.31 (dd, 4H), 7.26 (d, 2H), 7.24 (s, 6H), 7.22 (d, 6H), 7.20 (d, 4H), 7.08 (m, 11H), 7.02-6.98 (m, 5H). The above results confirmed that the obtained product was the objective product.
Comparative example 1 device preparation example:
the organic light-emitting device is prepared by a vacuum thermal evaporation method. The experimental steps are as follows: and (3) putting the ITO transparent substrate into distilled water for cleaning for 3 times, ultrasonically cleaning for 15 minutes, after the cleaning of the distilled water is finished, ultrasonically cleaning solvents such as isopropanol, acetone, methanol and the like in sequence, drying at 120 ℃, drying, and conveying to an evaporation plating machine.
Evaporating a hole injection layer HAT-CN/50nm, a hole transport layer NPB/30nm and an evaporation main body ADN on the prepared ITO-Ag-ITO electrode in a layer-by-layer vacuum evaporation mode: doping BD 5% mixed/30 nm, then evaporating an electron transport layer Alq 3 : liq (1)Layer material Alq 3 A wavelength of 60nm. And the device was sealed in a glove box, thereby preparing an organic light emitting device. After the organic light-emitting device is manufactured according to the steps, the photoelectric property of the device is measured, and the molecular structural formula of the related material is as follows:
comparative example 2 device preparation example:
the capping layer material Alq in comparative example 1 3 The compound was replaced with CP-1.
Device examples 1 to 9
Device example 1: the capping layer material in the organic light emitting device of comparative example 1 was changed to compound 1 in synthesis example 1 of the present invention.
Device example 2: the capping layer material in the organic light emitting device of comparative example 1 was changed to the compound 24 in synthesis example 2 of the present invention.
Device example 3: the capping layer material in the organic light emitting device of comparative example 1 was changed to compound 29 in synthesis example 3 of the present invention.
Device example 4: the capping layer material in the organic light emitting device of comparative example 1 was changed to compound 35 in synthesis example 4 of the present invention.
Device example 5: the material of the cap layer in the organic light emitting device of comparative example 1 was changed to the compound 43 in synthesis example 5 of the present invention.
Device example 6: the capping layer material in the organic light emitting device of comparative example 1 was changed to the compound 62 in synthesis example 6 of the present invention.
Device example 7: the material of the cap layer in the organic light emitting device of comparative example 1 was changed to the compound 119 in synthetic example 7 of the present invention.
Device example 8: the capping layer material in the organic light emitting device of comparative example 1 was changed to the compound 126 in synthesis example 8 of the present invention.
Device example 9: the capping layer material in the organic light emitting device of comparative example 1 was changed to the compound 129 in synthesis example 9 of the present invention.
The test software, computer, K2400 digital source meter manufactured by Keithley corporation, usa, and PR788 spectral scanning luminance meter manufactured by Photo Research corporation, usa were combined into a joint I-V-L test system to test the luminous efficiency and CIE color coordinates of the organic light emitting device. The results of the light emitting characteristic test of the obtained organic light emitting device are shown in table 1. Table 1 shows the results of the test of the light emitting characteristics of the compounds prepared in the examples of the present invention and the light emitting devices prepared in the comparative examples.
Table 1 test of light emitting characteristics of light emitting device
From the above table data, the currently applied Alq is compared 3 The amine compound has high luminous efficiency, is applied to a covering layer of an OLED device, and can effectively improve the luminous efficiency of the organic light-emitting device.
It is obvious that the above description of the embodiments is only intended to assist the understanding of the method of the invention and its core ideas. It should be noted that, for those skilled in the art, without departing from the principle of the present invention, it is possible to make various improvements and modifications to the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
Claims (6)
1. An amine compound, which is characterized by being represented by a general formula I,
wherein Ar is 1 Selected from formula II:
wherein X is selected from O, S and NR 0 Wherein R is 0 One selected from phenyl and tolyl;
R 1 、R 2 、R 3 、R 4 is selected from H;
L 0 selected from unsubstituted phenylene;
Ar 2 independently selected from phenyl or one of the following groups:
Ar 3 、Ar 5 independently selected from phenyl or one of the following groups:
Ar 4 、Ar 6 independently selected from phenyl or one of the following groups:
L 1 、L 2 、L 3 one selected from single bond and phenylene;
r is selected from hydrogen;
n is selected from one of 0,1, 2 and 3.
2. The amine compound of claim 1, wherein the general formula i is selected from the group consisting of formula i-a, formula i-c, formula i-f, and formula i-g:
3. the amine compound of claim 1, wherein formula ii is selected from the group consisting of the following formulae ii-a to ii-c:
4. the amine compound of claim 1, wherein L is 0 One selected from the group consisting of the following formula V-1, formula V-5, formula V-6:
5. an amine compound, wherein the amine compound is selected from one of the following chemical structures:
6. an organic light emitting device, comprising a cathode, an anode and one or more organic layers, wherein the organic layers comprise one or more organic layers disposed between and outside the two electrodes, and the organic layers comprise at least one of a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, and a capping layer; wherein the organic layer comprises a covering layer containing any one or a combination of at least two of the amine compounds according to any one of claims 1 to 5.
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