CN110729418A - Organic electroluminescent device and display device - Google Patents
Organic electroluminescent device and display device Download PDFInfo
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- CN110729418A CN110729418A CN201911014301.9A CN201911014301A CN110729418A CN 110729418 A CN110729418 A CN 110729418A CN 201911014301 A CN201911014301 A CN 201911014301A CN 110729418 A CN110729418 A CN 110729418A
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- organic electroluminescent
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- electroluminescent device
- dye
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- 239000000463 material Substances 0.000 claims abstract description 86
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- 125000004093 cyano group Chemical group *C#N 0.000 claims description 12
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- 125000001424 substituent group Chemical group 0.000 claims description 11
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- JHYLKGDXMUDNEO-UHFFFAOYSA-N [Mg].[In] Chemical compound [Mg].[In] JHYLKGDXMUDNEO-UHFFFAOYSA-N 0.000 description 1
- OEMGCAOEZNBNAE-UHFFFAOYSA-N [P].[Li] Chemical compound [P].[Li] OEMGCAOEZNBNAE-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- LPTWEDZIPSKWDG-UHFFFAOYSA-N benzenesulfonic acid;dodecane Chemical compound OS(=O)(=O)C1=CC=CC=C1.CCCCCCCCCCCC LPTWEDZIPSKWDG-UHFFFAOYSA-N 0.000 description 1
- PPTSBERGOGHCHC-UHFFFAOYSA-N boron lithium Chemical compound [Li].[B] PPTSBERGOGHCHC-UHFFFAOYSA-N 0.000 description 1
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Inorganic materials [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 1
- 125000004623 carbolinyl group Chemical group 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 238000004770 highest occupied molecular orbital Methods 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Inorganic materials [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 1
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 1
- 238000001748 luminescence spectrum Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- SJCKRGFTWFGHGZ-UHFFFAOYSA-N magnesium silver Chemical compound [Mg].[Ag] SJCKRGFTWFGHGZ-UHFFFAOYSA-N 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000006263 metalation reaction Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 125000005328 phosphinyl group Chemical group [PH2](=O)* 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical class N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229920000553 poly(phenylenevinylene) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
-
- 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
-
- 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
- H10K85/636—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising heteroaromatic 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
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
Landscapes
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention provides an organic electroluminescent device and a display device, wherein a luminescent layer of the organic electroluminescent device comprises a host material, a sensitizer and a dye; the host material is a wide band gap material, the sensitizer is a thermally activated delayed fluorescence material, and the dye is a boron-nitrogen material shown in formula 1. The organic electroluminescent device of the present invention has excellent efficiency and color purity.
Description
Technical Field
The invention relates to an organic electroluminescent device and a display device, and belongs to the technical field of organic electroluminescence.
Background
An Organic Light Emitting Diode (OLED) is a device that emits Light by current driving, and has the main characteristics that when a proper voltage is applied, electrons and holes combine in the Organic Light Emitting layer to generate excitons and emit Light with different wavelengths according to the characteristics of the Organic Light Emitting layer. At this stage, the light emitting layer is composed of a host material and a dopant dye, and the conventional fluorescent material has a defect that triplet excitons cannot be utilized, so that the internal quantum efficiency cannot be broken through by 25%.
Compared with the traditional fluorescent material, the Thermal Activated Delayed Fluorescence (TADF) material can realize the reverse system jump of triplet excitons to singlet states by absorbing environmental heat, so that the traditional fluorescent light emission is mainly Sensitized by doping a TADF sensitizer through a host material, namely, a Thermal Activated Sensitized Fluorescence (TASF) mechanism.
However, even if the TASF mechanism is adopted, the blue TASF device still suffers from the problems of low efficiency of the deep blue device (CIEy <0.15) and insufficient color purity of the device.
Disclosure of Invention
The invention provides an organic electroluminescent device, which can effectively improve the efficiency and color purity of the organic electroluminescent device by regulating and controlling the composition of a light-emitting layer of the device.
The present invention also provides a display device having excellent efficiency and color purity since it includes the above organic electroluminescent device.
The invention provides an organic electroluminescent device, wherein a luminescent layer comprises a host material, a sensitizer and a dye;
the host material is a wide band gap material, the sensitizer is a thermally activated delayed fluorescence material, and the dye is a boron-nitrogen material shown in a formula 1;
wherein, Y1、Y2And Y3Each independently selected from H or B, and at most one of which is H;
X1、X2and X3Each independently selected from N or H, and at most one of which is H;
X4、X5and X6Each independently selected from H, a single bond, O, S or CRaWhen X is present4、X5And X6Each independently selected from H, up to two are H, wherein R isaEach independently selected from one of the following substituted or unsubstituted groups: C1-C10 alkyl, C6-C30 monocyclic aromatic hydrocarbon or polycyclic aromatic hydrocarbon, C5-C30 monocyclic heteroaromatic hydrocarbon or polycyclic heteroaromatic hydrocarbon;
Z1、Z2、Z3、Z4、Z5、Z6、Z7、Z8、Z9、Z10、Z11、Z12、Z13、Z14、Z15、Z16、Z17、Z18each independently selected from N or CRbWherein R isbEach independently selected from hydrogen, deuterium, halogen, cyano, or one of the following substituted or unsubstituted groups: C1-C36 alkyl, C2-C6 alkenyl, C1-C6 alkoxy or thioalkoxy, C6-C48 monocyclic aromatic hydrocarbon or fused ring aromatic hydrocarbon, C3-C48 monocyclic heteroaromatic hydrocarbon or fused ring heteroaromatic hydrocarbon, and two adjacent groups RbIndependently of one another or at least two adjacent radicals RbCyclanes of C3-C10, arenes of C6-C30, or heteroarenes of C5-C30 bonded to each other;
Z19is selected from N or C;
when the above groups have substituents, the substituents are respectively and independently selected from one of deuterium, cyano, halogen, alkyl or cycloalkyl of C1-C10, alkenyl or cycloalkenyl of C2-C6, alkoxy or thioalkoxy of C1-C6, nitro, amino, carbonyl, carboxyl, ester group, aryl of C6-C30, and heteroaryl of C3-C30.
Optionally, the boron-nitrogen material is a structure shown in formula 1-1 or formula 1-2,
wherein Z is1、Z2、Z3、Z4、Z5、Z6、Z7、Z8、Z9、Z10、Z11、Z12、Z13、Z14、Z15、Z16、Z17、Z18Each independently selected from N or CRb；
Z19Is selected from N or C.
Alternatively, Z1、Z2、Z3、Z4、Z5、Z6、Z7、Z8、Z9、Z10、Z11、Z12、Z13、Z14、Z15、Z16、Z17、Z18、Z19Up to six of which are N atoms.
Alternatively, Z1、Z2、Z3、Z4、Z5、Z6、Z7、Z8、Z9、Z10、Z11、Z12、Z13、Z14、Z15、Z16、Z17、Z18、Z19Up to three of which are N atoms.
Alternatively, in formulae 1-1 and 1-2, Z2、Z5、Z8、Z11、Z14、Z17At least one of them is an N atom.
Alternatively, the R isbEach independently selected from: hydrogen, deuterium, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, cyclopentyl, neopentyl, n-hexyl, cyclohexyl, neohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2,2, 2-trifluoroethyl, methoxy, phenyl, naphthyl, anthracenyl, benzanthryl, phenanthryl, benzophenanthryl, pyrenyl, bornyl, perylenyl, fluoranthenyl, tetracenyl, pentacenyl, benzopyrenyl, biphenyl, biphenylyl, terphenyl, quaterphenyl, fluorenyl, spirobifluorenyl, dihydrophenanthryl, dihydropyrenyl, tetrahydropyrenyl, cis-or trans-indenofluorenyl, trimeric indenyl, isotridecyl, spiroindenyl, spiroisotridecyl, furyl, furanyl, pentakis, 2-trifluoroethyl, 2, 2-trifluoroethyl, methoxy, phenyl, naphthyl, anthracenyl, phenanthrenyl, terphenyl, terp, Benzofuranyl, isobenzofuranyl, dibenzofuranyl, thienyl, methylSubstituted thienyl, benzothienyl, isobenzothienyl, dibenzothienyl, pyrrolyl, isoindolyl, carbazolyl, indenocarbazolyl, pyridyl, methyl-substituted pyridyl, quinolyl, isoquinolyl, acridinyl, phenanthridinyl, benzo-5, 6-quinolyl, benzo-6, 7-quinolyl, benzo-7, 8-quinolyl, pyrazolyl, indazolyl, imidazolyl, benzimidazolyl, naphthoimidazolyl, phenanthroimidazolyl, pyridoimidazolyl, pyrazinoimidazolyl, quinoxalinyl, oxazolyl, benzoxazolyl, naphthooxazolyl, anthraoxazolyl, phenanthroizolyl, 1, 2-thiazolyl, 1, 3-thiazolyl, benzothiazolyl, pyridazinyl, benzopyrazinyl, pyrimidinyl, benzopyrimidinyl, quinoxalyl, 1, 5-diazahnthrylyl, 2, 7-diazenylene group, 2, 3-diazenylene group, 1, 6-diazenylene group, 1, 8-diazenylene group, 4,5,9, 10-tetraazaperyl group, pyrazinyl group, phenazinyl group, phenothiazinyl group, naphthyridinyl group, azacarbazolyl group, benzocarbazinyl group, phenanthrolinyl group, 1,2, 3-triazolyl group, 1,2, 4-triazolyl group, benzotriazolyl group, 1,2, 3-oxadiazolyl group, 1,2, 4-oxadiazolyl group, 1,2, 5-oxadiazolyl group, 1,2, 3-thiadiazolyl group, 1,2, 4-thiadiazolyl group, 1,2, 5-thiadiazolyl group, 1,3, 4-thiadiazolyl group, 1,3, 5-triazinyl group, 1,2, 4-triazinyl group, 1, one of 2, 3-triazinyl, tetrazolyl, 1,2,4, 5-tetrazinyl, 1,2,3, 4-tetrazinyl, 1,2,3, 5-tetrazinyl, purinyl, pteridinyl, indolizinyl, benzothiadiazolyl, 9-dimethylazinyl, (poly) halobenzene, (poly) cyanobenzene, (poly) trifluoromethylbenzene, or a combination of two substituent groups selected therefrom.
Optionally, the boron-nitrogen material is selected from compounds having one of the structures shown by A-1 to A-150 in the invention.
Optionally, the dye is present in the light-emitting layer in a proportion of 0.1 to 20% by mass.
Optionally, the host material is a compound comprising a carbazole group and the sensitizer is a compound comprising a cyano group.
The invention also provides a display device comprising any one of the organic electroluminescent devices.
The energy level difference between the singlet state and the triplet state of the dye shown in the formula 1 is low, so that triplet excitons are easy to be converted upwards and transferred to the singlet state, and therefore, the organic electroluminescent device can effectively utilize the triplet excitons of the dye on the basis of a TASF (TaSF) light emitting mechanism, so that the efficiency of the device can be further improved; in addition, the dye shown in the formula 1 has the characteristic of narrow spectrum of an emitting electrode due to a special structure, so that the color purity of the organic electroluminescent device is favorably improved.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The organic electroluminescent device comprises an anode, a hole transport region, a luminescent layer, an electron transport region and a cathode which are sequentially deposited on a substrate.
The substrate, the anode, the hole transport region, the electron transport region, and the cathode may be made of materials commonly used in the art. For example, a glass or polymer material having excellent mechanical strength, thermal stability, water resistance, and transparency; the anode material can be Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), and tin dioxide (SnO)2) Oxide transparent conductive materials such as zinc oxide (ZnO), and any combination thereof; the cathode may be made of magnesium (Mg), silver (Ag), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag), or any combination thereof.
The light-emitting layer will be described in detail below.
The invention provides an organic electroluminescent device, wherein a luminescent layer comprises a host material, a sensitizer and a dye;
the host material is a wide band gap material, the sensitizer is a thermally activated delayed fluorescence material, and the dye is a boron-nitrogen material shown in a formula 1;
wherein, Y1、Y2And Y3Each independently selected from H or B, and at most one of which is H;
X1、X2and X3Each independently selected from N or H, and at most one of which is H;
X4、X5and X6Each independently selected from H, a single bond, O, S or CRaWhen X is present4、X5And X6Each independently selected from H, up to two are H, wherein R isaEach independently selected from one of the following substituted or unsubstituted groups: C1-C10 alkyl, C6-C30 monocyclic aromatic hydrocarbon or polycyclic aromatic hydrocarbon, C5-C30 monocyclic heteroaromatic hydrocarbon or polycyclic heteroaromatic hydrocarbon;
Z1、Z2、Z3、Z4、Z5、Z6、Z7、Z8、Z9、Z10、Z11、Z12、Z13、Z14、Z15、Z16、Z17、Z18each independently selected from N or CRbWherein R isbEach independently selected from hydrogen, deuterium, halogen, cyano, or one of the following substituted or unsubstituted groups: C1-C36 alkyl, C2-C6 alkenyl, C1-C6 alkoxy or thioalkoxy, C6-C48 monocyclic aromatic hydrocarbon or fused ring aromatic hydrocarbon, C3-C48 monocyclic heteroaromatic hydrocarbon or fused ring heteroaromatic hydrocarbon, and two adjacent groups RbIndependently of one another or at least two adjacent radicals RbCyclanes of C3-C10, arenes of C6-C30, or heteroarenes of C5-C30 bonded to each other;
Z19is selected from N or C;
when the above groups have substituents, the substituents are respectively and independently selected from one of deuterium, cyano, halogen, alkyl or cycloalkyl of C1-C10, alkenyl or cycloalkenyl of C2-C6, alkoxy or thioalkoxy of C1-C6, nitro, amino, carbonyl, carboxyl, ester group, aryl of C6-C30, and heteroaryl of C3-C30.
In the formula 1, Y1、Y2And Y3At least two of which are B atoms, X1、X2And X3At least two of which are N atoms;
when X is present4、X5And X6Independently of each other from the H atom, up to two of them may simultaneously be hydrogen atoms, i.e. at least one must be a single bond, O, S or CRa；
Z19Selected from N atoms or C atoms, it being understood that when Z is19Selected from the N atoms, then Z19No linkage to any group other than the heteroatom as a central pyridine;
further, RbEach independently selected from hydrogen, deuterium, halogen, cyano, or one of the following substituted or unsubstituted groups: C1-C36 alkyl, further C1-C10 alkyl; alkenyl of C2-C6; alkoxy or thioalkoxy of C1-C6; C6-C48 monocyclic aromatic hydrocarbon or polycyclic aromatic hydrocarbon, further C6-C30 monocyclic aromatic hydrocarbon or polycyclic aromatic hydrocarbon; C3-C48 monocyclic heteroaromatic hydrocarbon or condensed ring heteroaromatic hydrocarbon, further C3-C30 monocyclic heteroaromatic hydrocarbon or condensed ring heteroaromatic hydrocarbon; two radicals R adjacent to each otherbMay be independent of one another without any linking relationship, or at least two adjacent radicals RbCan be bonded to each other to form C3-C10 cycloalkane, C6-C30 arene or C5-C30 heteroarene, wherein two adjacent R' sbMeans to two RbThe attached carbon atoms have a bonding relationship;
when R isaAnd RbWhen having substituents, the substituents are respectively and independently selected from deuterium, cyano, halogen, C1-C10 alkyl or cycloalkyl, C2-C6 alkenyl or cycloalkenyl, C1-C6 alkoxy or thioalkoxy, nitro, amino, carbonyl, carboxyl, ester group, C6-C30 aryl (including monocyclic aryl or fused ring aryl), and C3-C30 heteroaryl (including monocyclic heteroaryl or fused ring heteroaryl).
As can be understood from the above description, the boron-nitrogen material represented by formula 1 of the present invention can be classified into three types. The first type is: z1、Z2、Z3、Z4、Z5、Z6、Z7、Z8、Z9、Z10、Z11、Z12、Z13、Z14、Z15、Z16、Z17、Z18、Z19Are all independently selected from CRb(ii) a The second type is Z1、Z2、Z3、Z4、Z5、Z6、Z7、Z8、Z9、Z10、Z11、Z12、Z13、Z14、Z15、Z16、Z17、Z18、Z19All are selected from N; the third type is Z1、Z2、Z3、Z4、Z5、Z6、Z7、Z8、Z9、Z10、Z11、Z12、Z13、Z14、Z15、Z16、Z17、Z18、Z19Containing both N atoms and the same or different CRb. In particular applications, the boron-nitrogen material may be any one of the three materials described above.
The organic electroluminescent device utilizes a TASF light-emitting mechanism, namely, a three-doping mode of a main body material, a TADF material sensitizer and a fluorescent dye is adopted. The difference is that 2-3 boron atoms are introduced into the dye, so that the energy level difference between a singlet state and a triplet state is reduced, triplet state excitons are more easily subjected to up-conversion and singlet state transfer to generate delayed fluorescence, and holes and electrons are combined in a light emitting layer and then accompany the sensitizer and the dye
The generation of energy transfer (wherein the singlet excitons of the sensitizer comprise singlet excitons themselves, triplet excitons which are up-converted to themselves, and the host material to the sensitizer
Excitons for energy transfer and Dexter energy transfer), triplet excitons of the boron-nitrogen material are also easy to be converted upwards and transferred to singlet states, so that the device not only can effectively utilize excitons of a host material and a sensitizer to sensitize dye to emit light, but also can effectively utilize triplet excitons of the dye, thereby having excellent device efficiency;
in addition, according to the technical scheme provided by the invention, the boron-nitrogen material with the composition is used as a dye, so that the blue color purity of the organic electroluminescent device can be obviously improved. The inventors have analyzed based on this phenomenon and considered that it is possible to: according to the boron-nitrogen material, 2-3 boron atoms are introduced into 2,4 and 6 positions of a benzene ring or a pyridine ring, so that the electron-withdrawing capability of molecules is increased to a certain extent, and a donor snap ring of adjacent carbazole derivatives is formed, so that the HOMO-LOMO of a molecular structure is concentrated, the plane conjugation is good, and no obvious intramolecular charge transfer excited state exists in the molecule, and therefore a narrow light-emitting spectrum can be obtained, the narrowing of the spectrum of a device is facilitated, and the color purity of the device is improved; meanwhile, rigid carbazole, phenoxazine or phenothiazine and a derivative donor thereof are respectively introduced into 1,3 and 5 positions of a central benzene ring or pyridine ring of the boron-nitrogen material, and the rigid carbazole, phenoxazine or phenothiazine and derivative donors thereof are matched with 2-3 boron atoms to increase the molecular rigidity, so that the vibration relaxation of the boron-nitrogen material can be further reduced, and the spectrum can be subjected to blue shift; when X is present4、X5And X6When at most two of the hydrogen atoms are hydrogen atoms, the coordination rigidity of the ligand and the central boron atom can be further increased, unnecessary oscillation energy loss is reduced, and the luminous efficiency is improved.
Moreover, when the boron-nitrogen material is selected from the second or third materials, the improvement of the device efficiency is more remarkable, and may be: because a ligand containing N heterocycle is introduced into the boron-nitrogen material and is matched with B atom, the improvement of molecular electronegativity is facilitated, and the regulation and control effect on HOMO/LUMO energy level of the compound are achieved, so that the electron transmission capability of molecules can be changed to a large extent, and the further improvement of device efficiency is facilitated.
Further, the boron-nitrogen material of the invention can be a structure shown in formula 1-1 or formula 1-2,
wherein Z is1、Z2、Z3、Z4、Z5、Z6、Z7、Z8、Z9、Z10、Z11、Z12、Z13、Z14、Z15、Z16、Z17、Z18Each independently selected from N or CRb，RbAs with the previous definition, no further description is provided herein;
in the formula 1-2, Z19Is selected from N or C.
Specifically in the formula 1-1, Y1、Y2And Y3All selected from B atoms, and X1、X2And X3All selected from N atoms;
in the formula 1-2, Y1、Y2And Y3Two of which are selected from B atoms, one is a H atom, and X is1、X2And X3All selected from N atoms.
In one embodiment, Z in formula 1, formula 1-1, and formula 1-21、Z2、Z3、Z4、Z5、Z6、Z7、Z8、Z9、Z10、Z11、Z12、Z13、Z14、Z15、Z16、Z17、Z18、Z19When containing N atoms, it contains at most six nitrogen atoms, and the rest are CRb. The compound with the structure can further improve the electron transport performance of the material, so that the performance of a device is improved, if N heteroatom is excessive, the difficulty of coordination with B is increased, and the stability of the molecular structure is insufficient; and the synthesis difficulty is high, which is not beneficial to large-scale production. Further, when Z in formula 1, formula 1-1 and formula 1-21、Z2、Z3、Z4、Z5、Z6、Z7、Z8、Z9、Z10、Z11、Z12、Z13、Z14、Z15、Z16、Z17、Z18、Z19Contains at most three nitrogen atoms when the nitrogen atom is contained in the composition.
In order to optimize the degree of matching between the N-heterocyclic ligand and the B atom in the boron-nitrogen material, the inventors have adjusted the N-heterocyclic ligand, and found that when the N atom in the N-heterocyclic ligand is at the γ position in the carbazolyl group, the degree of matching between the N-ligand and the B atom at the specific N-heterocyclic position is optimal, which is very beneficial to improving the electron transport capability of the molecule, and further improves the efficiency of the device. Specifically, in formula 1, formula 1-1 and formula 1-2, Z2、Z5、Z8、Z11、Z14、Z17At least one of them is an N atom.
When Z in the present invention1、Z2、Z3、Z4、Z5、Z6、Z7、Z8、Z9、Z10、Z11、Z12、Z13、Z14、Z15、Z16、Z17、Z18At least one of which is CRbWhen R isbEach independently selected from: hydrogen, deuterium, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, cyclopentyl, neopentyl, n-hexyl, cyclohexyl, neohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2,2, 2-trifluoroethyl, methoxy, phenyl, naphthyl, anthracenyl, benzanthryl, phenanthryl, benzophenanthryl, pyrenyl, bornyl, perylenyl, fluoranthenyl, tetracenyl, pentacenyl, benzopyrenyl, biphenyl, biphenylyl, terphenyl, quaterphenyl, fluorenyl, spirobifluorenyl, dihydrophenanthryl, dihydropyrenyl, tetrahydropyrenyl, cis-or trans-indenofluorenyl, trimeric indenyl, isotridecyl, spiroindenyl, spiroisotridecyl, furyl, furanyl, pentakis, 2-trifluoroethyl, 2, 2-trifluoroethyl, methoxy, phenyl, naphthyl, anthracenyl, phenanthrenyl, terphenyl, terp, Benzofuranyl, isobenzofuranyl, dibenzofuranyl, thienyl, methyl-substituted thienyl, benzothienyl, isobenzothienyl, diBenzothienyl, pyrrolyl, isoindolyl, carbazolyl, indenocarbazolyl, pyridyl, methyl-substituted pyridyl, quinolyl, isoquinolyl, acridinyl, phenanthridinyl, benzo-5, 6-quinolyl, benzo-6, 7-quinolyl, benzo-7, 8-quinolyl, pyrazolyl, indazolyl, imidazolyl, benzimidazolyl, naphthoimidazolyl, phenanthrimidazolyl, pyridoimidazolyl, pyrazinoimidazolyl, quinoxalinyl, oxazolyl, benzoxazolyl, naphthooxazolyl, anthraoxazolyl, phenanthroxazolyl, 1, 2-thiazolyl, 1, 3-thiazolyl, benzothiazolyl, pyridazinyl, benzopyrdazinyl, pyrimidinyl, benzopyrimidinyl, quinoxalinyl, 1, 5-diazaanthrenyl, 2, 7-diazapyrenyl, 2, 3-diazpyrenyl, 1, 6-diazenyl, 1, 8-diazenyl, 4,5,9, 10-tetraazaperylene, pyrazinyl, phenazinyl, phenothiazinyl, naphthyridinyl, azacarbazolyl, benzocarbazinyl, phenanthrolinyl, 1,2, 3-triazolyl, 1,2, 4-triazolyl, benzotriazolyl, 1,2, 3-oxadiazolyl, 1,2, 4-oxadiazolyl, 1,2, 5-oxadiazolyl, 1,2, 3-thiadiazolyl, 1,2, 4-thiadiazolyl, 1,2, 5-thiadiazolyl, 1,3, 4-thiadiazolyl, 1,3, 5-triazinyl, 1,2, 4-triazinyl, 1,2, 3-triazinyl, tetrazolyl, 1, 6-diazenyl, 1, 8-diazenyl, 4-triazinyl, 1,2, 3-triazinyl, 1,2, 5-thiadiazolyl, 1, 3-thia, 1,2,4, 5-tetrazinyl, 1,2,3, 4-tetrazinyl, 1,2,3, 5-tetrazinyl, purinyl, pteridinyl, indolizinyl, benzothiadiazolyl, 9-dimethylazinyl, (poly) halobenzene, (poly) cyanobenzene, (poly) trifluoromethylbenzene, or a combination of two substituents selected from the above.
Specifically, the boron-nitrogen material of the present invention is preferably a compound having one of the following structures:
the host material and the sensitizer material are not particularly limited, and the wide-bandgap material of the host material may be a compound including at least one group selected from carbazolyl, carbolinyl, spirofluorenyl, fluorenyl, silicon base, and phosphinyl.
In particular embodiments, the host material may preferably be a compound having one of the following structures:
further, the TADF material as a sensitizer in the present invention is also not particularly limited, and may be any material having a difference in singlet and triplet energy levels of less than 0.3eV, and for example, a compound represented by any one of the following may be preferable:
in addition, the performance of the device can be further optimized by controlling the mass ratio of the sensitizer and the dye in the light-emitting layer.
In the implementation process of the invention, the mass ratio of the dye in the luminescent layer is generally controlled to be more than 0.01%. The doping amount of the dye in the luminescent layer is reasonably controlled, which is beneficial to further improving the efficiency and the color purity of the device, so that the mass content of the dye can be controlled to be more than 0.1%. The inventor researches and discovers that as the proportion of the dye in the light-emitting layer is increased within a certain range, the efficiency and the color purity of the device are gradually improved and then basically kept unchanged or slightly reduced, so that the proportion of the dye in the light-emitting layer is generally controlled to be 0.1-20% in terms of performance optimization and preparation economy.
Of course, the use of different host materials and sensitizers in the light emitting layer can have an impact on the performance of the device. Therefore, in general, for the different host materials and sensitizers, when the mass ratio of the dye in the light-emitting layer is controlled to be 0.5% to 5%, the device can be ensured to have excellent efficiency and color purity.
In addition, when the mass ratio of the dye in the luminescent layer is controlled to be 0.5-5%, the mass ratio of the sensitizer in the luminescent layer can be 1-50%, and the rest is the host material, so as to ensure the efficient sensitization degree of the dye.
Further, the inventors have studied the matching between the host material and the sensitizer and the dye represented by formula 1 of the present invention, and found that when the host material is a compound containing a carbazolyl group and the sensitizer material is a compound containing a cyano group, the efficiency and color purity of the device can be further improved.
The hole transport region, the electron transport region, and the cathode of the present invention will be described below. The hole transport region is located between the anode and the light emitting layer. The hole transport region may be a Hole Transport Layer (HTL) of a single layer structure including a single layer containing only one compound and a single layer containing a plurality of compounds. The hole transport region may also be a multilayer structure including at least two layers of a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), and an Electron Blocking Layer (EBL).
The materials of the hole transport region, including HIL, HTL and EBL, may be selected from, but are not limited to, phthalocyanine derivatives such as CuPc, conductive polymers or polymers containing conductive dopants such as polyphenylenevinylene, polyaniline/dodecylbenzenesulfonic acid (Pani/DBSA), poly (3, 4-ethylenedioxythiophene)/poly (4-styrenesulfonate) (PEDOT/PSS), polyaniline/camphorsulfonic acid (Pani/CSA), polyaniline/poly (4-styrenesulfonate) (Pani/PSS), aromatic amine derivatives.
Wherein the aromatic amine derivatives are compounds represented by HT-1 to HT-34 below. If the material of the hole transport region 3 is an aromatic amine derivative, it may be one or more of compounds represented by HT-1 to HT-34.
The hole injection layer is located between the anode and the hole transport layer. The hole injection layer may be a single compound material or a combination of a plurality of compounds. For example, the hole injection layer may employ one or more compounds of HT-1 to HT-34 described above, or one or more compounds of HI1-HI3 described below; one or more of the compounds HT-1 to HT-34 may also be used to dope one or more of the compounds HI1-HI3 described below.
The electron transport region may be an Electron Transport Layer (ETL) of a single-layer structure including a single-layer electron transport layer containing only one compound and a single-layer electron transport layer containing a plurality of compounds. The electron transport region may also be a multilayer structure including at least two layers of an Electron Injection Layer (EIL), an Electron Transport Layer (ETL), and a Hole Blocking Layer (HBL).
In one aspect of the invention, the electron transport layer material may be selected from, but is not limited to, the combination of one or more of ET-1 through ET-57 listed below.
The light emitting device may further include an electron injection layer between the electron transport layer and the cathode in the structure, and the electron injection layer includes, but is not limited to, one or more of the following combinations.
LiQ,LiF,NaCl,CsF,Li2O,Cs2CO3,BaO,Na,Li,Ca。
The thicknesses of the various layers described above may be those conventional in the art.
The invention also provides a preparation method of the organic electroluminescent device, which comprises the steps of depositing the anode, the hole transmission area, the luminescent layer, the electron transmission area and the cathode on the substrate in sequence, and then packaging. When the luminescent layer is prepared, the evaporation rate of the main body material, the sensitizer and the dye is adjusted by using a multi-source co-evaporation method so that the dye reaches a preset doping proportion, and the luminescent layer is formed by using a wide-band-gap material source, a TADF material source and any one of the boron-nitrogen material sources through co-evaporation. And the anode, the hole transport region, the electron transport region and the cathode are deposited in the same manner as the prior art.
The embodiment of the invention also provides a display device which comprises the organic electroluminescent device provided as above. The display device can be specifically a display device such as an OLED display, and any product or component with a display function including the display device, such as a television, a digital camera, a mobile phone, a tablet computer, and the like. The display device has the same advantages as the organic electroluminescent device compared with the prior art, and the description is omitted here.
Specific preparation methods of the boron-nitrogen material of the present invention will be described in detail below by taking a plurality of synthesis examples as examples, but the preparation method of the present invention is not limited to these synthesis examples.
Basic chemical raw materials of various chemicals used in the present invention, such as petroleum ether, tert-butylbenzene, ethyl acetate, sodium sulfate, toluene, dichloromethane, potassium carbonate, boron tribromide, N-diisopropylethylamine, reaction intermediate, and the like, are commercially available from shanghai tatarian technologies ltd and silong chemical ltd. The mass spectrometer used for determining the following compounds was a ZAB-HS type mass spectrometer measurement (manufactured by Micromass, UK).
In the following, briefly explaining the method for synthesizing a boron-nitrogen material represented by formula 1 of the present invention (scheme (1)), first, X is synthesized using n-butyllithium, t-butyllithium or the like1、X2And X3The hydrogen atoms in between undergo ortho-metallation. Subsequently, boron tribromide, phosphorus trichloride, or the like is added to perform metal exchange of lithium-boron or lithium-phosphorus, and then a Bronsted base (e.g., N-diisopropylethylamine) is added to perform a Tandem boro-Friedel-Crafts Reaction (Tandem Bora-Friedel-Crafts Reaction), whereby a target product can be obtained.
More specifically, the following gives a synthetic method of a representative specific compound of the present invention.
Synthetic examples
Synthesis example 1: synthesis of Compound A-9
Under nitrogen atmosphere, a pentane solution of tert-butyllithium (18.96mL, 1.60M, 30.34mmol) was slowly added to a solution of Br-substituted precursor A-9-1(13.62g, 13.79mmol) in tert-butylbenzene (150mL) at 0 deg.C, and then the temperature was sequentially raised to 80 deg.C, 100 deg.C, and 120 deg.C for 1 hour each. After the reaction was complete, the temperature was reduced to-30 ℃ and boron tribromide (7.6g, 30.34mmol) was slowly added and stirring was continued at room temperature for 0.5 hour. N, N-diisopropylethylamine (5.35g, 41.37mmol) was added at room temperature and the reaction was continued at 145 ℃ for 5 hours and stopped. The solvent was dried by evaporation in vacuo and passed through a silica gel column (developing solvent: ethyl acetate: petroleum ether: 50:1) to give the title compound C-9(1.00g, 8% yield, HPLC assay purity 99.56%) as a yellow solid. MALDI-TOF-MS results: molecular ion peaks: 926.45 elemental analysis results: theoretical value: 85.62 percent of C; 7.51 percent of H; b, 2.33 percent; 4.545 percent of N; experimental values: 85.72 percent of C; 7.66 percent of H; 2.83 percent of B; and 3.79 percent of N.
Synthesis example 2: synthesis of Compound A-29
This example is substantially the same as synthetic example 1 except that: in this case, A-9-1 is replaced by A-29-1 in an equal amount. The title compound A-29(1.29g, 10% yield, 99.36% purity by HPLC) was a yellow solid. MALDI-TOF-MS results: molecular ion peaks: 923.31 elemental analysis results: theoretical value: c, 85.82%; h, 4.26%; b, 2.34%; n, 7.58%; experimental values: c, 85.83%; h, 4.25%; b, 2.24%; and N,7.68 percent.
Synthetic example 3: synthesis of Compound A-51
This example is substantially the same as synthetic example 1 except that: in this case, A-9-1 is replaced by A-51-1 in an equal amount. The title compound A-51(0.92g, 10% yield, 99.55% purity by HPLC) was a yellow solid. MALDI-TOF-MS results: molecular ion peaks: 665.62 elemental analysis results: theoretical value: c, 86.65%; h, 3.79%; b, 3.25%; n, 6.32%; experimental values: c, 86.85%; h, 3.59%; b, 3.05%; n,6.52 percent.
Synthetic example 4: synthesis of Compound A-63
This example is substantially the same as synthetic example 1 except that: in this case, A-9-1 is replaced by A-63-1 in an equal amount. The title compound A-63(0.90g, 10% yield, 99.55% purity by HPLC) was a yellow solid. MALDI-TOF-MS results: molecular ion peaks: 655.48 elemental analysis results: theoretical value: c, 76.97%; h, 3.54%; b,3.30 percent; n, 6.41%; s, 9.78%; experimental values: c, 76.77%; h, 3.74%; b, 3.50%; n, 6.31%; s,9.68 percent.
Synthesis example 5: synthesis of Compound A-91
Under a nitrogen atmosphere, a solution of tert-butyllithium in pentane (31.03mL, 1.60M, 49.64mmol) was slowly added to a solution of A-91-1(9.0g, 13.79mmol) in tert-butylbenzene (150mL) at 0 ℃ and the temperature was raised to 80 ℃ and 100 ℃ and 120 ℃ in this order for 1 hour each. After the reaction was complete, the temperature was reduced to-30 ℃ and boron tribromide (12.43g, 49.64mmol) was slowly added and stirring continued at room temperature for 0.5 h. N, N-diisopropylethylamine (8.99g, 41.37mmol) was added at room temperature and the reaction was continued at 145 ℃ for 5 hours and stopped. The solvent was dried by evaporation in vacuo and passed through a silica gel column (developing solvent: ethyl acetate: petroleum ether: 50:1) to give the title compound a-91(0.60g, 7.3% yield, 99.56% purity by HPLC) as a yellow solid. MALDI-TOF-MS results: molecular ion peaks: 597.68 elemental analysis results: theoretical value: 84.49 percent of C; h, 3.04 percent; 5.43 percent of B; 7.04 percent of N; experimental values: 84.64 percent of C; 3.35 percent of H; b, 4.83 percent; and 7.18 percent of N.
Synthesis example 6 Synthesis of Compound A-78:
(1) preparation of intermediate A-78-1:
to a 1L single neck flask was added γ -carboline (38.3g, 227.9mmol, 2.2eq), 1-bromo-3, 5-difluorobenzene (50.36g, 103.60mmol, 1eq), cesium carbonate (148.5g, 455.8mmol, 4.5eq), N-dimethylformamide (600mL) at room temperature under nitrogen, and reacted at 120 ℃ overnight.
Stopping heating, adding 1000mL of water after cooling to room temperature, stirring for 10min, precipitating a large amount of light white solid, and performing suction filtration, wherein the PE is that EA is 30:1, and carrying out column chromatography to obtain 44.9g of white solid, namely the intermediate A-78-1.
(2) Preparation of intermediate A-78-2:
intermediate A-78-1(24.4g, 50mmol, 1q), diphenylamine (9.3g, 55mmol, 1.1eq), Pd were added at room temperature2(dba)3(2.54g, 2.5mmol, 0.05eq), s-Phos (2.05g, 5mmol, 0.1eq), sodium tert-butoxide (21.6g, 225mmol, 4.5eq), toluene (500mL) were charged in a 1000mL single vial, nitrogen was purged three times, and the vial was heated to 130 ℃ for reaction overnight.
The reaction mixture was cooled to room temperature and filtered through celite. The filtrate was concentrated, and dichloromethane was added to dissolve and mix with silica gel to concentrate, and column chromatography (PE: EA ═ 30:1) was performed to obtain 29.6g of crude white solid, and ethanol was added to boil and wash for 3 hours to obtain 26.6g of white solid product, i.e., intermediate a-78-2.
(3) Preparation of Compound A-78:
a pentane solution of n-butyllithium (23mL, 36.68mmol, 1.6M) was added dropwise to a solution of intermediate A-78-2(8.82g, 15.3mmol) in 4-tert-butyltoluene (200mL) in an ice bath under nitrogen, and after the addition was complete, the mixture was stirred in the ice bath for 10 minutes and then transferred to an oil bath at 80 ℃ for reaction. After 4 hours of reaction, the temperature is reduced to room temperature, the temperature is cooled to below minus 40 ℃, boron tribromide (4.36mL, 11.5g and 46mmol) is taken out by a needle tube and rapidly added into the system, and the reaction is gradually returned to the room temperature for 1 hour. N, N-diisopropylethylamine (10.76mL, 7.9g, 61.2mol) was added to the system by syringe under ice bath and then transferred to an oil bath for reaction at 130 ℃ for 5 hours. Cooling to room temperature, vacuum filtering with Buchner funnel filled with diatomaceous earth, concentrating the filtrate under reduced pressure, adding dichloromethane, dissolving, mixing with silica gel, concentrating, and preparing for column chromatography.
Column chromatography (PE/DCM ═ 25:1) gave 5.9g crude yellow solid, which was boiled in 50mL of n-hexane for 5h to give 4.8g yellow solid, which was passed through the column by TLC (PE/EA ═ 50:1) several times to give about 1.6g pure product, compound a-78, 99.8% pure.
Structural characterization:
mass spectrum molecular weight theoretical value: 593.26, molecular weight detection value: 593.21.
theoretical value of elemental analysis: c, 80.98%; h, 3.57%; n, 11.81%, elemental analysis test value: c, 80.85%; h, 3.91%; n, 12.10%
The organic electroluminescent device according to the invention is further illustrated by the following specific examples.
Examples 1 to 29
Examples 1 to 29 each provide an organic electroluminescent device having a device structure including an ITO anode, a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an emission layer (EML), an Electron Transport Layer (ETL), an Electron Injection Layer (EIL), and a cathode in this order.
The material of the hole injection layer is HI-3, the total thickness is generally 1-10nm, and the thickness is 2nm in this embodiment. The hole transport layer is made of HT-28, and has a total thickness of 5-50nm, 30nm in this embodiment. The host material of the light-emitting layer is a wide band gap material, the sensitizer is TADF, the dye is a boron-nitrogen material represented by formula 1, and the thickness of the light-emitting layer is generally 1-60nm, in this embodiment 30 nm. The material of the electron transport layer is ET-52, and the thickness is generally 5-30nm, and 25nm in the embodiment. The material of the electron injection layer is LiQ (1nm), and the material of the cathode is Al (150 nm).
Examples 1 to 29 provide organic electroluminescent devices in which the specific selection and doping concentrations (mass ratio in the light-emitting layer) of the host material, sensitizer and dye are shown in table 1.
Comparative examples 1 to 4
Comparative examples 1 to 4 provide organic electroluminescent devices having device structures in accordance with examples 1 to 29, and parameters of respective functional layers in accordance with examples 1 to 29, except that the host material, sensitizer and dye used material of the light-emitting layer or doping concentration were not uniform. The specific dye materials of comparative examples were selected as shown in the following A-151 and A-152.
The following tests were carried out on the devices of the examples and comparative examples, the results of which are shown in Table 1.
1. The following performance measurements were made on the organic electroluminescent devices (examples 1 to 29, comparative examples 1 to 4) prepared by the above procedure: the characteristics of the prepared device such as current, voltage, brightness, luminescence spectrum, current efficiency, external quantum efficiency and the like are synchronously tested by adopting a PR655 spectrum scanning luminance meter and a Keithley K2400 digital source meter system, and the service life of the device is tested through an MC-6000 test.
2. The life test for LT50@500nit is as follows: the brightness and life decay curve of the organic electroluminescent device is obtained by setting different test brightness, so that the life value of the device under the condition of the required decay brightness is obtained. I.e. setting the test luminance to 500cd/m2The luminance drop of the organic electroluminescent device was measured to be 250cd/m while maintaining a constant current2Time in hours.
TABLE 1
As can be seen from Table 1:
1. compared with a comparative example, when the compound shown in the formula 1 is used as a dye in the luminescent layer, the half-peak width of the organic electroluminescent device is narrower, so that better color purity is shown, meanwhile, the luminous efficiency is obviously improved, and the overall characteristic of the organic electroluminescent device is obviously superior to that of the comparative example;
2. as can be seen from the comparison between examples 21 to 22 and other examples, when the wide band gap material of the light-emitting layer contains a carbazole group and TADF of the sensitizer contains a cyano group, the dye matching property with the dye represented by formula 1 of the present invention is better, and the half-peak width and the light-emitting efficiency of the organic electroluminescent device can be improved more advantageously;
3. as can be seen from comparison of examples 1 to 28 with example 29, the device is superior in lifetime, half-peak width and luminous efficiency when the proportion of the dye of the present invention in the light emitting layer is 0.1 wt% to 20 wt%, and the device is superior in lifetime, half-peak width and luminous efficiency when the proportion of the dye of the present invention in the light emitting layer is 0.5 wt% to 5 wt%.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. An organic electroluminescent device, characterized in that a light-emitting layer comprises a host material, a sensitizer and a dye;
the host material is a wide band gap material, the sensitizer is a thermally activated delayed fluorescence material, and the dye is a boron-nitrogen material shown in a formula 1;
wherein, Y1、Y2And Y3Each independently selected from H or B, and at most one of which is H;
X1、X2and X3Each independently selected from N or H, and at most one of which is H;
X4、X5and X6Each independently selected from H, a single bond, O, S or CRaWhen X is present4、X5And X6Each independently selected from H, up to two are H, wherein R isaEach independently selected from one of the following substituted or unsubstituted groups: C1-C10 alkyl, C6-C30 monocyclic aromatic hydrocarbon or polycyclic aromatic hydrocarbon, C5-C30 monocyclic heteroaromatic hydrocarbon or polycyclic heteroaromatic hydrocarbon;
Z1、Z2、Z3、Z4、Z5、Z6、Z7、Z8、Z9、Z10、Z11、Z12、Z13、Z14、Z15、Z16、Z17、Z18each independently selected from N or CRbWherein R isbEach independently selected from hydrogen, deuterium, halogen, cyano, or one of the following substituted or unsubstituted groups: C1-C36 alkyl, C2-C6 alkenyl, C1-C6 alkoxy or thioalkoxy, C6-C48 monocyclic aromatic hydrocarbon or fused ring aromatic hydrocarbon, C3-C48 monocyclic heteroaromatic hydrocarbon or fused ring heteroaromatic hydrocarbon, and two adjacent groups RbIndependently of one another or at least two adjacent radicals RbCyclanes of C3-C10, arenes of C6-C30, or heteroarenes of C5-C30 bonded to each other;
Z19is selected from N or C;
when the above groups have substituents, the substituents are respectively and independently selected from one of deuterium, cyano, halogen, alkyl or cycloalkyl of C1-C10, alkenyl or cycloalkenyl of C2-C6, alkoxy or thioalkoxy of C1-C6, nitro, amino, carbonyl, carboxyl, ester group, aryl of C6-C30, and heteroaryl of C3-C30.
2. The organic electroluminescent device according to claim 1, wherein the boron-nitrogen material is a structure represented by formula 1-1 or formula 1-2,
wherein Z is1、Z2、Z3、Z4、Z5、Z6、Z7、Z8、Z9、Z10、Z11、Z12、Z13、Z14、Z15、Z16、Z17、Z18Each independently selected from N or CRb；
Z19Is selected from N or C.
3. The organic electroluminescent device according to claim 1 or 2, wherein Z is1、Z2、Z3、Z4、Z5、Z6、Z7、Z8、Z9、Z10、Z11、Z12、Z13、Z14、Z15、Z16、Z17、Z18、Z19Up to six of which are N atoms.
4. The organic electroluminescent device of claim 3, wherein Z is1、Z2、Z3、Z4、Z5、Z6、Z7、Z8、Z9、Z10、Z11、Z12、Z13、Z14、Z15、Z16、Z17、Z18、Z19Up to three of which are N atoms.
5. According to claimThe organic electroluminescent element as claimed in claim 2, wherein in formulae 1-1 and 1-2, Z is2、Z5、Z8、Z11、Z14、Z17At least one of them is an N atom.
6. The organic electroluminescent device according to claims 1 to 5, wherein R isbEach independently selected from: hydrogen, deuterium, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, cyclopentyl, neopentyl, n-hexyl, cyclohexyl, neohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2,2, 2-trifluoroethyl, methoxy, phenyl, naphthyl, anthracenyl, benzanthryl, phenanthryl, benzophenanthryl, pyrenyl, bornyl, perylenyl, fluoranthenyl, tetracenyl, pentacenyl, benzopyrenyl, biphenyl, biphenylyl, terphenyl, quaterphenyl, fluorenyl, spirobifluorenyl, dihydrophenanthryl, dihydropyrenyl, tetrahydropyrenyl, cis-or trans-indenofluorenyl, trimeric indenyl, isotridecyl, spiroindenyl, spiroisotridecyl, furyl, furanyl, pentakis, 2-trifluoroethyl, 2, 2-trifluoroethyl, methoxy, phenyl, naphthyl, anthracenyl, phenanthrenyl, terphenyl, terp, Benzofuranyl, isobenzofuranyl, dibenzofuranyl, thienyl, methyl-substituted thienyl, benzothienyl, isobenzothienyl, dibenzothienyl, pyrrolyl, isoindolyl, carbazolyl, indenocarbazolyl, pyridyl, methyl-substituted pyridyl, quinolyl, isoquinolyl, acridinyl, phenanthridinyl, benzo-5, 6-quinolyl, benzo-6, 7-quinolyl, benzo-7, 8-quinolyl, pyrazolyl, indazolyl, imidazolyl, benzimidazolyl, naphthoimidazolyl, phenanthroimidazolyl, pyridoimidazolyl, pyrazinoimidazolyl, quinoxaloiyl, oxazolyl, benzoxazolyl, naphthooxazolyl, anthraoxazolyl, phenanthroizolyl, 1, 2-thiazolyl, 1, 3-thiazolyl, benzothiazolyl, pyridazinyl, phenanthrolinyl, 1, 2-thiazolyl, 1, 3-thiazolyl, benzothiazolyl, and phenanthrolinyl, A benzopyrazinyl group, a pyrimidinyl group, a benzopyrimidinyl group, a quinoxalinyl group, a 1, 5-diazanthryl group, a 2, 7-diazpyrenyl group, a 2, 3-diazpyrenyl group, a 1, 6-diazpyrenyl group, a 1, 8-diazpyrenyl group, a 4,5,9, 10-tetraazaperylene group, a substituted perylene group,Pyrazinyl, phenazinyl, phenothiazinyl, naphthyridinyl, azacarbazolyl, benzocarbazinyl, phenanthrolinyl, 1,2, 3-triazolyl, 1,2, 4-triazolyl, benzotriazolyl, 1,2, 3-oxadiazolyl, 1,2, 4-oxadiazolyl, 1,2, 5-oxadiazolyl, 1,2, 3-thiadiazolyl, 1,2, 4-thiadiazolyl, 1,2, 5-thiadiazolyl, 1,3, 4-thiadiazolyl, 1,3, 5-triazinyl, 1,2, 4-triazinyl, 1,2, 3-triazinyl, tetrazolyl, 1,2,4, 5-tetrazinyl, 1,2,3, 4-tetrazinyl, 1,2,3, 5-tetrazinyl, purinyl, pteridinyl, indolizinyl, benzothiadiazinyl, 9, 9-dimethyl acridine group, (poly) halogenated benzene, (poly) cyanobenzene, (poly) trifluoromethyl benzene, or a combination of two substituent groups.
7. The organic electroluminescent device according to claim 1 or 2, wherein the boron-nitrogen material is selected from compounds represented by the following structures,
8. the organic electroluminescent device according to any one of claims 1 to 7, wherein the dye is present in the light-emitting layer in a proportion of 0.1 to 20% by mass.
9. The organic electroluminescent device according to claim 8, wherein the host material is a compound comprising a carbazole group, and the sensitizer is a compound comprising a cyano group.
10. A display device comprising the organic electroluminescent element as claimed in any one of claims 1 to 9.
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