CN113429336B - Organic electroluminescent material, light-emitting device and application - Google Patents
Organic electroluminescent material, light-emitting device and application Download PDFInfo
- Publication number
- CN113429336B CN113429336B CN202110833125.2A CN202110833125A CN113429336B CN 113429336 B CN113429336 B CN 113429336B CN 202110833125 A CN202110833125 A CN 202110833125A CN 113429336 B CN113429336 B CN 113429336B
- Authority
- CN
- China
- Prior art keywords
- organic electroluminescent
- light
- electroluminescent material
- organic
- emitting layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/10—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a carbon chain containing aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
-
- 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
- H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
-
- 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
-
- 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
- H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1059—Heterocyclic compounds characterised by ligands containing three nitrogen atoms as heteroatoms
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Optics & Photonics (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The disclosure provides an organic electroluminescent material, a light-emitting device and uses thereof. The organic electroluminescent material takes triphenylethylene as a core and comprises donor groups such as carbazole and the like and acceptor groups such as cyano or azine and the like. The organic electroluminescent device comprises an anode, a cathode and an organic functional layer formed between the anode and the cathode, wherein the organic functional layer comprises a light-emitting layer, and the light-emitting layer comprises the organic electroluminescent material, so that the organic electroluminescent device has good blue light emitting performance and aggregation-induced light emitting characteristic, can improve the problems of low light emitting efficiency, low stability and the like.
Description
Technical Field
The invention relates to the technical field of organic light emitting diodes, in particular to an organic electroluminescent material, a light emitting device and application.
Background
An Organic Light-Emitting Diode (OLED) is an Organic electroluminescent device using an Organic semiconductor material as a hole or electron transport medium and a Light-Emitting active layer. Compared with an electroluminescent device prepared from an inorganic semiconductor material, the OLED prepared from the organic semiconductor material has the advantages of solid-state luminescence, surface luminescence, low cost, environmental friendliness, flexibility and the like, and has a wide application prospect in the fields of display and illumination. For example, the OLED display panel has the advantages of lightness, thinness, high brightness, high contrast, high-definition display, power saving, energy saving, and the like, and gradually becomes the mainstream display technology; the white light OLED lighting device has the advantages of eye protection with low blue light, anti-glare, light color close to sunlight, random design of the light-emitting panel and the like.
The luminescent material in the existing organic electroluminescent device has poor luminescent performance.
Disclosure of Invention
In view of the above, the present invention is directed to an organic electroluminescent material, a light emitting device and a use thereof.
The embodiment of the present disclosure provides an organic electroluminescent material, which has a structure of formula (I):
wherein Y is CR1;
each R1 is independently selected from H, D, F, cl, br, I, NR 2 、CN、NO 2 、SiR 3 、B(OR) 2 、 C(＝O)R、P(＝O)R 2 、S(＝O)R、S(＝O) 2 R、OSO 2 R、C 1～40 Linear alkyl or alkoxy or thioalkoxy, C 2～40 Linear alkenyl or alkynyl of (2), C 3～40 At least one of a branched or cyclic alkyl or alkenyl or alkynyl or alkoxy or alkylalkoxy or thioalkoxy group of (a), an aryl or heteroaryl group containing 5 to 60 ring atoms, an aryloxy or arylalkoxy or heteroaryloxy group containing 5 to 60 ring atoms, or a diarylamino or diheteroarylamino or arylheteroarylamino group containing 10 to 40 ring atoms;
wherein R is benzene or a benzene homologue and derivative;
ar is CN or an organic electron transporting group of an electron deficient heteroaromatic group;
x is CR2; wherein each R2 is independently selected from H or an electron-rich organic group that conducts holes.
In some embodiments, the hole-conducting, electron-rich group has the structure of formula (II), formula (III), or formula (IV); wherein each Z is independently selected from N, O or S; * Is connected with C;
wherein each Z is independently selected from N, O or S; * Indicating attachment to C.
In some embodiments, each R1 is independently selected from H or C 1～6 An alkyl group.
In some embodiments, each R1 is independently selected from H or C 1～3 An alkyl group.
In some embodiments, the organic electron transporting group of the electron deficient heteroaromatic group is selected from triazine, pyrimidine, pyrazine, pyridine, quinazoline, benzimidazole, quinoline, isoquinoline, or naphthyridine.
In some embodiments, the electron deficient heteroaromatic group is a triazine.
In some embodiments, each Z is independently selected from N or O.
In some embodiments, the C 1～40 Linear alkyl or alkoxy or thioalkoxy of, said C 2～40 Linear alkenyl or alkynyl of (A), C 3～40 Optionally one or more H on the branched or cyclic alkyl or alkenyl or alkynyl or alkoxy or alkylalkoxy or thioalkoxy group of (A) is substituted by R, or one or more non-adjacent CH 2 The radicals being RC = CR, C ≡ C, siR 2 、GeR 2 、SnR 2 、C＝O、C ＝S、C＝Se、C＝NR、P(＝O)R、SO、SO 2 NR, O, S or CONR and one or more of H in the substituted groups is/are D, F, cl, br, I, CN or NO 2 And (4) substitution.
In some embodiments, the aryl or heteroaryl of 5 to 60 ring atoms, the aryloxy, arylalkoxy, or heteroaryloxy of 5 to 60 ring atoms is optionally substituted with one or more H by R.
In some embodiments, the 10 to 40 ring atom diarylamino or diheteroarylamino or arylheteroarylamino group is optionally substituted with one or more H by R or a combination of two or more R.
In some embodiments, in the combination of two or more R's, two or more adjacent R's form a mono-or polycyclic, aliphatic or aromatic ring system with each other.
In some embodiments, the organic electroluminescent material has at least one of the following structural formulas:
the embodiment of the present disclosure further provides an organic electroluminescent device, which includes an anode, a cathode, and an organic functional layer formed between the anode and the cathode, where the organic functional layer includes a light-emitting layer, and the light-emitting layer includes the organic electroluminescent material as described in any one of the foregoing.
In some embodiments, the mass fraction of the organic electroluminescent material in the organic electroluminescent layer is 10 to 30%.
In some embodiments, the organic electroluminescent material is present in the organic electroluminescent layer in a mass fraction of 15 to 25%.
In some embodiments, the light emitting layer further comprises a host material selected from at least one of CBP and mCBP.
In some embodiments, the organic functional layer further includes a hole transport layer and an electron transport layer, which are respectively stacked on both surfaces of the light emitting layer.
The embodiment of the disclosure also provides a use of the organic electroluminescent material as described in any one of the above items in preparing a light-emitting layer.
The organic electroluminescent material provided by the embodiment of the present disclosure is prepared by designing an organic electron transport group Ar (i.e., an electron donor), such as CN or an organic electron transport group X of an electron-deficient heteroaromatic group, in a compound molecular structure with phenylethene having aggregation-induced emission characteristics, and cooperatively designing an electron-rich organic group X (i.e., an electron acceptor), such as H or an electron-rich organic group conducting a hole; can effectively separate HOMO on an electron donor from LUMO electron cloud on an electron acceptor, thereby inducing the electron donor to generate smaller delta E ST Value to be effectiveRISC (Reverse Intersystem Cross) Reverse system Crossing. Meanwhile, due to steric hindrance and intermolecular interaction in an aggregation state, the molecular motion such as intramolecular rotation, intramolecular vibration and the like of a twisted molecular structure of the compound is limited, so that the energy proportion dissipated through the motion form is reduced, the energy proportion of a light output form is increased, the intermolecular pi-pi interaction in the aggregation state is weakened, concentration quenching and exciton quenching are improved, and then extremely high photoluminescence quantum yield of solid PLQY (photoluminescence quantum yield) is obtained, and strong blue fluorescence is emitted. After being applied to an organic electroluminescent device, the organic electroluminescent device has good electroluminescent performance.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the following detailed description is given with reference to specific embodiments.
Materials for an Emission layer (EML) in an organic electroluminescent device such as an OLED generally include a host material and a guest material. The host material generally includes a P-type host material and an N-type host material, the P-type host material is a hole transport type material, and the N-type host material is an electron transport type material; the P-type host material is mainly provided with an electron donating group, and the N-type host material is mainly provided with an electron withdrawing group. The guest materials mainly comprise fluorescent luminescent materials and phosphorescent luminescent materials, red light and green light in most of the currently applied organic electroluminescent devices mainly comprise the phosphorescent luminescent materials, and blue light still mainly comprises the fluorescent luminescent materials.
Each adjacent material layer in the organic film layer in the organic electroluminescent device needs to meet certain energy level collocation, namely the HOMO energy level and LUMO energy level difference between the organic film layers must meet the barrier condition of electron or hole transmission. Generally speaking, the HOMO energy level of the hole transport layer material must be gradually increased from the anode to the light emitting layer, while the LUMO energy level of the electron transport layer material must be gradually decreased from the cathode to the light emitting layer, so as to reduce the barrier for hole and electron transport, and make the hole and electron smoothly reach the light emitting layer and combine to generate exciton, thereby achieving the purpose of light emission. The triplet state and singlet state energy levels of the host luminescent material and the guest luminescent material are also important to match, the singlet state and triplet state energy levels of the host luminescent material should be higher than that of the guest luminescent material, so that excitons are prevented from flowing back into the host luminescent material from the guest luminescent material, the excitons in the host luminescent material are unidirectionally transferred to the guest luminescent material to enable the guest luminescent material to emit light, and the luminous efficiency is improved.
According to spin quantum statistics, electron/hole pairs generated by a fluorescent light emitting material under current excitation generate singlet and triplet excitons in a ratio of 1. In a closed-shell purely organic system, singlet excitons can rapidly de-excite to fluoresce, and triplet excitons can only return to the ground state in a non-radiative transition due to spin-forbidden confinement. Therefore, the conventional fluorescent light emitting material can emit light only with 25% of singlet excitons, and 75% of triplet excitons are inactivated in a non-radiative manner. Whereas a small energy range Delta E is required in the molecular design process of a Thermally Activated Delayed Fluorescence (TADF) ST For efficient RISC, the Highest Occupied Molecular Orbital (HOMO) and the Lowest Unoccupied Molecular Orbital (LUMO) need to be sufficiently separated, which leads to a reduced dipole moment of the transition and a reduced radiative efficiency, so that the photoluminescence quantum yield (PLQY) of the TADF molecule is not high overall.
The fluorescence of the traditional fluorescent chromophore can be reduced or even not emitted under high concentration, and the main reason of concentration quenching is related to the formation of aggregates. Many organic molecules emit light strongly in dilute solution due to their planar conjugated structure, but their fluorescence becomes weak or even disappears completely in high concentration solution or in aggregated (nanoparticles, micelles, solid films or powders) state, which is a concentration-quenching effect (ACQ) phenomenon, i.e. the more general aggregation causes quenching. Most of the pi-pi conjugated emitters are subject to aggregation-induced quenching (ACQ) effect in the aggregation state, resulting in a decrease in the luminous efficiency and stability of the OLED. Therefore, due to its own conjugated structure, most conventional TADF molecules are quenched after aggregation due to pi-pi stacking between the molecules, i.e., an aggregation-induced quenching effect is generated.
According to the luminescent material, common traditional luminescent groups are modified by triphenylethylene, and the triphenylethylene is combined with carbazole and other groups, so that the luminescent material with high solid-state luminous efficiency and excellent hole transport capacity can be obtained. Effectively improving the problem of fluorescence quenching caused by aggregation of the traditional luminescent group.
The embodiment of the disclosure provides an organic electroluminescent material, which has a structure of formula (I):
wherein Y is CR1; each R1 is independently selected from H, D, F, cl, br, I, NR 2 、 CN、NO 2 、SiR 3 、B(OR) 2 、C(＝O)R、P(＝O)R 2 、S(＝O)R、S(＝O) 2 R、OSO 2 R、 C 1～40 Linear alkyl or alkoxy or thioalkoxy of C 2～40 Linear alkenyl or alkynyl of (2), C 3～40 Or a branched or cyclic alkyl or alkenyl or alkynyl or alkoxy or alkylalkoxy or thioalkoxy group, an aryl or heteroaryl group of 5 to 60 ring atoms, an aryloxy or arylalkoxy or heteroaryloxy group of 5 to 60 ring atoms, or at least one of a diarylamino and diheteroarylamino or arylheteroarylamino group of 10 to 40 ring atoms. Wherein R is benzene or a benzene homologue and a derivative thereof.
Ar is CN or an organic electron-transporting group that is an electron-deficient heteroaromatic group.
X is CR2; each R2 is independently selected from H or an electron rich organic group that conducts holes.
In some embodiments, the C 1～40 Linear alkyl or alkoxy or thioalkoxy of C 2～40 Linear alkenyl or alkynyl of (2), C 3～40 Optionally one or more H on the branched or cyclic alkyl or alkenyl or alkynyl or alkoxy or alkylalkoxy or thioalkoxy group of (A) is substituted by R, or one or more non-adjacent CH 2 The radicals being selected from the group consisting of RC = CR, C ≡ C, siR 2 、GeR 2 、SnR 2 、C＝O、C＝S、C＝Se、 C＝NR、P(＝O)R、SO、SO 2 NR, O, S or CONR and one or more of the resulting groups H is/are substituted by D, F, cl, br, I, CN or NO 2 Substitution; the aryl or heteroaryl of 5 to 60 ring atoms, the aryloxy, arylalkoxy or heteroaryloxy of 5 to 60 ring atoms is optionally substituted by one or more H; the 10 to 40 ring atoms diarylamino or diheteroarylamino or arylheteroarylamino group is optionally substituted with one or more H by R or a combination of two R or a combination of more R; and in said combination of two or more R's, two or more adjacent R's form a mono-or polycyclic, aliphatic or aromatic ring system with each other. It should be noted that R refers to benzene or its homologues and derivatives.
In some embodiments, the electron-deficient heteroaromatic group is selected from one of triazine, pyrimidine, pyrazine, pyridine, quinazoline, benzimidazole, quinoline, isoquinoline, and naphthyridine.
In some embodiments, the hole-conducting, electron-rich group has a structure of formula (II), formula (III), or formula (IV); wherein each Z is independently selected from N, O or S; * Is connected to C.
According to the organic electroluminescent material provided by the embodiment of the disclosure, a unit part of an electron-rich organic group Ar (namely an electron acceptor) and an organic electron transport group (namely an electron donor) X is designed on a compound molecular structure through phenyl ethylene with aggregation-induced light emission characteristics, electron-rich groups such as CN, triazine, pyrimidine, pyrazine, pyridine, quinazoline, benzimidazole, quinoline, isoquinoline and naphthyridine are selected, and H or an organic electron transport group with a structure of formula (II) or formula (III) is selected in a matching manner; can effectively separate HOMO on an electron donor from LUMO electron cloud on an electron acceptor, thereby inducing the electron donor to generate smaller delta E ST To perform efficient RISC. Meanwhile, the twisted molecular structure of the compound disclosed by the invention rotates and divides in molecules under the aggregation state due to steric hindrance and intermolecular interactionThe molecular motion such as the intra-molecular vibration is limited, so that the energy proportion dissipated through the motion form is reduced, and the energy proportion of the light output form is increased, thereby weakening the pi-pi interaction between molecules in an aggregation state, improving the concentration quenching and exciton quenching, and further obtaining the extremely high solid PLQY; and simultaneously, a non-radiative transition channel is closed, excited state molecules return to a ground state in a radiative transition mode, and the excited state molecules are gathered to induce luminescence and emit strong blue fluorescence.
In some embodiments, each R1 is independently selected from H or C 1～6 An alkyl group. That is, in each Y of formula (I), each R1 is independently, and may be the same or different.
In some embodiments, each R1 is independently selected from H or C 1～3 An alkyl group.
In some embodiments, each R1 is independently selected from H or methyl.
In some embodiments, the electron deficient heteroaromatic group is a triazine. Each Z is independently selected from N or O. The novel blue organic electroluminescent material which takes triphenylethylene as a core, carbazolyl and the like as electron donors and is matched with cyano or triazine and the like as electron acceptors has better aggregation-induced emission effect, can further mutually constrain and limit the movement inside molecules in an aggregation state, further reduces the energy proportion dissipated due to a movement form, further increases the energy proportion of a light output form, and thus shows stronger fluorescence enhancement phenomenon and more efficient light emission; further improve the problems of low efficiency, poor stability and the like caused by fluorescence quenching and the like in a blue fluorescence system.
In some embodiments, the organic electroluminescent material has at least one of the following structural formulas:
the organic electroluminescent material with the structural formula has the advantages of simple and easily obtained synthetic raw materials, low cost, stable structure, better aggregation-induced light-emitting characteristic, good light-emitting efficiency and the like.
Based on the same inventive concept, the disclosed embodiment also provides the application of the organic electroluminescent material of the embodiment in preparing a light-emitting layer.
Based on the same inventive concept, the embodiment of the present disclosure further provides a light emitting layer, which includes the organic electroluminescent material.
In some embodiments, the light-emitting layer may be an undoped organic electroluminescent material as described above. That is, the light emitting layer is made of only the organic electroluminescent material of the above embodiment. In another embodiment, the light-emitting layer may also be a doped organic electroluminescent material as described above. That is, the light emitting layer is prepared by using the organic electroluminescent material and the host material of the above embodiments. The host material may be, for example, at least one of CBP (4, 4-bis (9-carbazole) biphenyl) and mCBP (3, 3 '-bis (9H-carbazol-9-yl) -1,1' -biphenyl).
In some embodiments, the mass fraction of the organic electroluminescent material in the organic electroluminescent layer is 10 to 30%. Namely, the weight ratio of the organic electroluminescent material to the host material is 1:9 to 3. By setting the organic electroluminescent material and the host material in the weight ratio, the luminescent layer can have better luminous efficiency and luminous life.
In some embodiments, the mass fraction of the organic electroluminescent material in the organic electroluminescent layer is 15 to 25%. Namely, the weight ratio of the organic electroluminescent material to the host material is 3: 17-1. The organic electroluminescent material and the main material can be further matched by the weight part ratio, so that the luminous efficiency and the luminous service life of the luminous layer are further improved.
Based on the same inventive concept, the embodiment of the present disclosure further provides a preparation method of the organic electroluminescent material of the above embodiment.
In some embodiments, when only one R1 is selected from methyl and the remaining R1 is selected from H, and Ar is selected from CN, the synthetic route of the organic electroluminescent material described above may be as follows:
wherein Z is independently selected from N or O.
Based on the same inventive concept, the disclosed embodiment also provides the application of the light-emitting layer of the embodiment in the preparation of an organic electroluminescent device.
Based on the same inventive concept, the embodiment of the present disclosure further provides an organic electroluminescent device, which includes an anode, a cathode, and an organic functional layer formed between the anode and the cathode, wherein the organic functional layer includes the light emitting layer of the above embodiment. That is, in the organic electroluminescent device, the light-emitting layer includes the organic electroluminescent material as described in any one of the foregoing.
It should be noted that, in the organic electroluminescent device, the light-emitting layer may be provided as one layer, or as two or more layers. When the light emitting layer is provided as two or more layers, the light emitting layers may be provided in a stack, and at least one light emitting layer includes the organic electroluminescent material as described in any one of the above.
In some embodiments, the anode is made of ITO-coated conductive glass, and the cathode is made of LiF/Al composite electrode.
In some embodiments, the light emitting layer further comprises a host material in the organic electroluminescent device. The host material can be at least one selected from CBP (4, 4-bis (9-carbazole) biphenyl) and mCBP (3, 3 '-bis (9H-carbazole-9-yl) -1,1' -biphenyl), and the mass fraction of the organic electroluminescent material in the organic electroluminescent layer is 10-30%. Namely, the weight ratio of the organic electroluminescent material to the host material is 1:9 to 3. By setting the organic electroluminescent material and the main material in the weight ratio, the luminescent layer can have better luminous efficiency and luminous life.
In some embodiments, the organic electroluminescent material in the organic electroluminescent device has a mass fraction of 15 to 25% in the organic electroluminescent layer. Namely, the weight ratio of the organic electroluminescent material to the host material is 3. The organic electroluminescent material and the main material can be further matched by the weight part ratio, so that the luminous efficiency and the luminous service life of the luminous layer are further improved.
In some embodiments, the organic functional layer further includes a hole injection layer, a hole transport layer, and an electron transport layer, which are sequentially stacked, and the hole transport layer and the electron transport layer are respectively stacked on both surfaces of the light emitting layer. The specific structures, material compositions and preparation methods of the hole injection layer, the hole transport layer and the electron transport layer of the embodiments of the present disclosure are the prior art, and the present disclosure does not relate to the improvement of the existing hole injection layer, hole transport layer and electron transport layer.
In some embodiments, the material of the Hole Injection (HIL) layer is HATCN; the material of the Hole Transport (HTL) layer is NPB; the material of the Electron Transport (ETL) layer is TPBI, and the host material of the light Emitting (EML) layer is CBP.
In specific implementation, a Hole Injection Layer (HIL) is arranged between the anode and the light-emitting layer, and a Hole Transport Layer (HTL) is arranged between the hole injection layer and the light-emitting layer; an electron transport layer (EBL) is disposed between the cathode and the light emitting layer. The structure of the organic electroluminescent device includes: the conductive glass plated with Indium Tin Oxide (ITO) is used as an anode, a Hole Injection Layer (HIL) (20 nm-30 nm), a Hole Transport Layer (HTL) (30 nm-40 nm), a light emitting layer (EML) (30 nm), an Electron Transport Layer (ETL) (30 nm), and a cathode adopts a LiF (1 nm)/Al (100 nm) composite electrode.
The structure of the organic electroluminescent device is specifically represented as: ITO/HATCN/NPB/Compound/TPBI/LiF/Al.
The following examples further illustrate the preparation of the organic electroluminescent material and the organic electroluminescent device of the present disclosure.
EXAMPLE 1 preparation of Compound 4
The synthetic route for compound 4 is as follows:
the specific preparation method of the compound 4 is as follows:
1.N 2 under the atmosphere, 12mmol of 9,9' - (5-bromo-1, 3-phenylene) bis (9H-carbazole) was added to dried tetrahydrofuran, the temperature was lowered to-60 ℃, t-BuLi (tert-Butyllithium) tert-Butyllithium (20 mL) was added dropwise to the system, the temperature was kept constant for 1H, and the reaction was stirred at room temperature for 8H. Then, the temperature of the system was lowered to-78 ℃, 36mmol of 4-methylbenzaldehyde was slowly dropped thereto, and the reaction was maintained for 1 hour, and further stirred at room temperature for 6 hours, after which the reaction was quenched with ice water, the organic layer was extracted with dichloromethane, and the pure compound (3, 5-Bis-carbazol-9-yl-phenyl) -p-tolyl-metha-nol) was obtained by column chromatography. ((3, 5-bis-carbazole-9-phenyl) -p-tolyl-methanol).
2. The resulting (3, 5-Bis-carbazol-9-yl-phenyl) -p-tolyl-methane was dissolved in 40mL of dichloromethane, and the oxidizing agent PCC was added to the system and reacted at room temperature for 8 hours. And (4) carrying out suction filtration and column separation and purification to obtain a product 2.
3. The resulting product 2 was placed in 45mL of dichloromethane, 8mL of phenylacetonitrile and 12mL of TiCl 4 The reaction was carried out at room temperature for 36 hours, and the organic layer was extracted with dichloromethane and dried. The product was purified by column chromatography to give compound 4.
1 HNMR(600MHz,CD 3 SO)：δ＝7.96(dd，J＝23.3，7.6Hz，4H)，7.93– 7.68(m，2H)，7.68–7.58(m，2H)，7.44(d，J＝19.0Hz，3H)，7.46– 7.26(m，8H)，7.24–7.09(m，6H)，7.03(dd，J＝17.9，10.6Hz，4H)， 2.38–2.24(m，2H). 13 CNMR(152MHz，CD 3 SO)δ1390.42，140.36，140. 09，139.47，139.25，130.82，130.19，129.89，129.97，129.67，129.59， 129.60，129.54，129.38，129.33，129.22，128.72，128.72，128.66，128. 44，128.41，128.20，127.81，127.67，127.39，126.99，126.39，126.30， 126.21，126.20，125.79，125.69，124.68，123.67，123.71，123.66，123. 60，120.60，120.49，120.39，120.39，109.77，109.69，109.40，21.47。
MS：(M，m/z)625.249.Anal.Calcd for C 46 H 31 N 3 ：C88.29％，H 4.99％and N 6.72％.Found：C88.31％，H 4.96％and N 6.71％。
EXAMPLE 2 preparation of Compound 21
The synthetic route for compound 21 is as follows:
the specific preparation method of compound 21 is as follows:
1.N 2 under the atmosphere, 12mmol of benzonaphthofuranyl carbazolyl substituted bromobenzene is added into dried tetrahydrofuran, the temperature is reduced to-60 ℃, t-BuLi (tert-Butyllithium) tert-butyl lithium (20 mL) is added into the system dropwise, the temperature is kept for 1h, and the reaction is stirred at room temperature for 8h. Then the temperature of the system is reduced to-78 ℃, 36mmol of 4-methylbenzaldehyde is slowly dripped into the system, the temperature is kept for reaction for 1h, the mixture is stirred for 6h at normal temperature, then ice water is used for quenching the reaction, dichloromethane is used for extracting an organic layer, and a product is separated by column chromatography to obtain an intermediate 1.
2. The resulting intermediate 1 was dissolved in 40mL of dichloromethane, and the oxidant PCC was added to the system, followed by reaction at room temperature for 8 hours. And (5) carrying out suction filtration, and carrying out column separation and purification on the product to obtain an intermediate 2.
3. Phenyl triazinyl ketone (5 mmol), intermediate 2 (5 mmol), and zinc powder (20 mmol) were added to 100mL anhydrous THF solvent under nitrogen atmosphere, and cooled to-78 deg.C. At this temperature TiCl is added dropwise 4 The solution (30 mmol) was warmed to room temperature and stirred for 1.5h, and then heated under reflux for 15h.Through K 2 CO 3 After the neutralization reaction, the crude product is separated and purified by column chromatography to obtain the final product compound 21.
1 HNMR(600MHz,CD 3 SO)：δ＝2.26(3H,s),7.37(2H,ddd,J＝8.2,1.5,0.4 Hz),7.50-7.61(3H,7.57(dddd,J＝6.9,6.0,1.8,0.4Hz),7.55(tdd,J＝6.0,1.6, 1.5Hz)),7.64-7.92(7H,7.68(ddd,J＝7.0,5.1,1.9Hz),7.71(ddd,J＝7.0,5.1, 1.8Hz),7.78(ddd,J＝8.2,1.6,0.4Hz),7.84(dddd,J＝6.9,1.8,1.6,0.4Hz), 7.88(tdd,J＝5.0,1.7,0.5Hz)),8.04(1H,tdd,J＝5.0,1.7,0.5Hz),8.15(1H,t,J ＝1.7Hz),8.21(1H,ddd,J＝1.8,0.5,0.5Hz),8.23(1H,dd,J＝2.0,0.4Hz),8.28 (1H,ddd,J＝5.1,1.9,0.5Hz),8.36(1H,dd,J＝5.1,0.5Hz),8.40-8.45(2H,8.43 (dd,J＝5.1,2.0Hz),8.42(ddt,J＝5.1,1.8,0.5Hz)),8.48-8.53(2H,8.52(dq,J＝ 1.8,0.5Hz),8.50(ddd,J＝5.1,0.5,0.4Hz)),8.64(1H,dd,J＝5.1,1.8Hz),8.74 (2H,d,J＝2.1Hz),8.86-8.96(4H,8.91(dddt,J＝5.0,1.8,1.7,0.5Hz),8.88(dd, J＝1.7,1.5Hz),8.87(dd,J＝1.7,1.5Hz),8.93(dddt,J＝5.0,1.8,1.7,0.5 Hz)),9.18(1H,dtt,J＝1.8,0.5,0.5Hz).
MS：(M，m/z)730.85.Anal.Calcd for C 52 H 34 N 4 O：C85.47％，H 4.71％， N7.65％and O2.17％.Found：C85.46％，H 4.69％,N 7.67％and O 2.19％。
Example 3 organic electroluminescent device 1
ITO/HATCN (30 nm)/NPB (30 nm)/Compound 4 (30 nm)/TPBI (30 nm)/LiF (2 nm)/Al (100 nm).
Wherein the material of the light-emitting layer is compound 4. That is, the light emitting layer is an undoped light emitting layer.
Example 4 organic electroluminescent device 2
ITO/HATCN (20 nm)/NPB (40 nm)/Compound 4 (20 wt%): CBP (30 nm)/TPBI (30 nm)/LiF (2 nm)/Al (100 nm).
Wherein, the light-emitting layer compound 4 (20 wt%): CBP indicates that the mass fraction of compound 4 in the light-emitting layer is 20%, that is, the light-emitting layer is a doped light-emitting layer.
Example 5 organic electroluminescent device 3
ITO/HATCN (30 nm)/NPB (30 nm)/Compound 21 (30 nm)/TPBI (30 nm)/LiF (2 nm)/Al (100 nm).
Example 6 organic electroluminescent device 4
ITO/HATCN (20 nm)/NPB (40 nm)/Compound 21 (20 wt%): CBP (30 nm)/TPBI (30 nm)/LiF (2 nm)/Al (100 nm).
Comparative example 1 organic electroluminescent device 5
ITO/HATCN(30nm)/NPB(30nm)/DPAVB(30nm)/TPBI(30nm) /LiF(2nm)/Al(100nm)。
Wherein, the material of the luminescent layer is DPAVB, and the structural formula is shown as the following formula 33. That is, this comparative example employs DPAVB instead of compound 4 of the organic light-emitting device 1 in example 3.
The organic electroluminescent devices of examples 3 to 6 and comparative example 1 were compared in terms of their properties, see table 1 below.
TABLE 1 Properties of organic electroluminescent devices of examples 3 to 6 and comparative example 1
| Device with a metal layer | Driving voltage (v) | Luminous efficiency (Cd/A) | Color coordinates (CIEx, CIEy) | Life span T97 (h) |
| Example 3 | 4.2 | 2.83 | (0.24，0.35) | 138 |
| Example 4 | 3.8 | 3.42 | (0.26，0.33) | 146 |
| Example 5 | 4.12 | 3.25 | (0.25，0.33) | 153 |
| Example 6 | 4.05 | 3.46 | (0.25，0.30) | 171 |
| Comparative example 1 | 4.47 | 6.59 | (0.18，0.24) | 42 |
The lifetime T97 is a time required for the fluorescence intensity to decrease to 97% of the maximum fluorescence intensity at the time of excitation.
As can be seen from table 1, compared to the conventional light-emitting material, the light-emitting device using compound 4 or compound 21 as the material of the light-emitting layer has a significantly improved light-emitting lifetime. The compound 4 and the compound 21 are used as dopants to prepare the luminescent layer by being matched with CBP, so that the luminescent life of the organic electroluminescent device is further prolonged compared with the luminescent life of a device which adopts the compound 4 or the compound 21 to prepare the luminescent layer. It can be seen that the organic electroluminescent material provided by the embodiments of the present disclosure, whether used as a dopant or used alone as a material of a light emitting layer, exhibits good electroluminescent performance.
The skilled person will understand that: the discussion of any embodiment above is meant to be exemplary only, and is not intended to intimate that the scope of the disclosure, including the claims, is limited to these examples; combinations of features of the above embodiments or different embodiments are possible within the inventive idea. Therefore, any omissions, modifications, substitutions, improvements and the like that may be made without departing from the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (8)
1. An organic electroluminescent material, characterized in that the organic electroluminescent material has a structure shown in formula (I):
wherein Y is CR1;
each R1 is independently selected from H, D, F, cl, br, I, NR 2 、CN、NO 2 、SiR 3 、B(OR) 2 、C(＝O)R、P(＝O)R 2 、S(＝O)R、S(＝O) 2 R、OSO 2 R、C 1～40 Linear alkyl or alkoxy or thioalkoxy, C 2～40 Linear alkenyl or alkynyl of (2), C 3～40 At least one of a branched or cyclic alkyl or alkenyl or alkynyl or alkoxy or alkylalkoxy or thioalkoxy group of (a), an aryl or heteroaryl group containing 5 to 60 ring atoms, an aryloxy or arylalkoxy or heteroaryloxy group containing 5 to 60 ring atoms, or a diarylamino or diheteroarylamino or arylheteroarylamino group containing 10 to 40 ring atoms;
wherein R is benzene;
ar is CN or triazine;
x is CR2; wherein each R2 is independently selectedFrom
* Indicating attachment to C.
2. The organic electroluminescent material according to claim 1, wherein R1 is independently selected from H and C 1～6 An alkyl group.
3. The organic electroluminescent material according to claim 1, wherein the organic electroluminescent material has at least one of the following structural formulas:
4. an organic electroluminescent device comprising an anode, a cathode and an organic functional layer formed between the anode and the cathode, wherein the organic functional layer comprises a light-emitting layer comprising the organic electroluminescent material according to any one of claims 1 to 3.
5. The organic electroluminescent device according to claim 4, wherein the organic electroluminescent material is present in the light-emitting layer in an amount of 10 to 30% by mass.
6. The organic electroluminescent device according to claim 5, wherein the mass fraction of the organic electroluminescent material in the light-emitting layer is 15 to 25%.
7. The organic electroluminescent device of claim 6, wherein the light-emitting layer further comprises a host material selected from at least one of CBP and mCBP.
8. Use of the organic electroluminescent material according to any one of claims 1 to 3 for the production of a light-emitting layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110833125.2A CN113429336B (en) | 2021-07-22 | 2021-07-22 | Organic electroluminescent material, light-emitting device and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110833125.2A CN113429336B (en) | 2021-07-22 | 2021-07-22 | Organic electroluminescent material, light-emitting device and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113429336A CN113429336A (en) | 2021-09-24 |
| CN113429336B true CN113429336B (en) | 2022-12-13 |
Family
ID=77761427
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110833125.2A Active CN113429336B (en) | 2021-07-22 | 2021-07-22 | Organic electroluminescent material, light-emitting device and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113429336B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114621210A (en) * | 2020-12-10 | 2022-06-14 | 湖南超亟检测技术有限责任公司 | Preparation method and application of novel fluorescent molecular probe for detecting L-cysteine |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001083410A1 (en) * | 2000-05-03 | 2001-11-08 | The Regents Of The University Of California | Soluble tetrahedral compounds for use in electroluminescent devices |
| CN101343537B (en) * | 2008-08-14 | 2012-05-09 | 中山大学 | Novel organic luminescent material containing triphenylethylene carbazole derivative structure |
| CN101659865B (en) * | 2009-09-16 | 2013-03-27 | 中山大学 | Gathering induced luminescence material containing triphenyl thylene structure, synthesis method and application thereof |
| CN101781234B (en) * | 2010-03-05 | 2013-04-03 | 淮海工学院 | Triphenylethylene compound containing cyanogen and preparation method thereof |
| CN101928559B (en) * | 2010-07-07 | 2014-02-19 | 中山大学 | Aggregation-induced light emitting material simultaneously containing triphenylethylene structure and tetraphenylethylene structure and synthesis method and application thereof |
| KR101950893B1 (en) * | 2012-12-20 | 2019-02-21 | 덕산네오룩스 주식회사 | Compound for organic electronic element, organic electronic element usingthe same, and a electronic device thereof |
| WO2015077836A1 (en) * | 2013-11-26 | 2015-06-04 | The University Of Melbourne | Solar concentrator |
| CN104860884B (en) * | 2015-05-19 | 2017-06-20 | 苏州大学 | Triphenylethylene-like derivatives and uses thereof |
| KR102294677B1 (en) * | 2015-06-11 | 2021-08-27 | 덕산네오룩스 주식회사 | Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof |
| CN107513075A (en) * | 2017-09-06 | 2017-12-26 | 山西大学 | The carbazole compound and its preparation of boron containing diaryl and triphenylethylene structure |
| EP3470398B1 (en) * | 2017-10-13 | 2022-05-04 | Novaled GmbH | Organic electronic device comprising an organic semiconductor layer |
| CN111072439A (en) * | 2019-11-25 | 2020-04-28 | 深圳大学 | Luminescent material and synthesis method and application thereof |
| CN113735739B (en) * | 2020-05-29 | 2023-01-06 | 香港科技大学 | Aggregation-induced emission stereoisomer, application and preparation method thereof |
-
2021
- 2021-07-22 CN CN202110833125.2A patent/CN113429336B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN113429336A (en) | 2021-09-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106892857B (en) | Thermal activation delayed fluorescent material and application thereof in organic electroluminescent device | |
| CN105503766B (en) | A kind of thermal activation delayed fluorescence material and organic electroluminescence device | |
| KR101742359B1 (en) | Organic electro luminescence device | |
| CN110444694B (en) | Compound and organic electroluminescent device | |
| WO2016042997A1 (en) | Organic electroluminescent element | |
| CN113336782B (en) | Green light narrow spectrum three-coordination boron luminescent compound containing carbazole skeleton, preparation method and application thereof | |
| CN108069951B (en) | Organic electroluminescent material based on benzoyl derivatives and preparation method thereof | |
| Wang et al. | Single molecular tuning of the charge balance in blue-emitting iridium dendrimers for efficient nondoped solution-processed phosphorescent OLEDs | |
| TW202100720A (en) | Melt mixture for organic electroluminescent element, and organic electroluminescent element | |
| CN107068880B (en) | A kind of organic electroluminescence device containing diaryl ketone compounds and its application | |
| Zhang et al. | Planarized intramolecular charge transfer on triphenylamine-modified pyrazine and its application in organic light-emitting diodes | |
| Zhu et al. | Anthracene-based bipolar deep-blue emitters for efficient white OLEDs with ultra-high stabilities of emission color and efficiency | |
| KR20240016253A (en) | Deuteride and organic electroluminescent devices | |
| KR20240016255A (en) | Deuteride and organic electroluminescent devices | |
| Lv et al. | Regulation of excited-state properties of dibenzothiophene-based fluorophores for realizing efficient deep-blue and HLCT-sensitized OLEDs | |
| CN113429336B (en) | Organic electroluminescent material, light-emitting device and application | |
| KR20230129396A (en) | Organic electroluminescent device and method of manufacturing the same | |
| KR102084990B1 (en) | Organic electroluminescent device using the same | |
| Sun et al. | Achieving highly efficient bipolar near-ultraviolet emitters via regulating the energy levels of the excited states by a co-acceptor system | |
| KR20190132261A (en) | Multicyclic compound and organic light emitting device comprising the same | |
| TW202003504A (en) | Organic electroluminescent element | |
| CN113991044A (en) | Green organic electroluminescent device and display device including the same | |
| TWI657081B (en) | An organic electroluminescent device containing a bipolar host material of a 1,2,4-triazine group | |
| WO2023008501A1 (en) | Organic electroluminescent element | |
| WO2024048535A1 (en) | Host material for organic electroluminescent elements, preliminary mixture, and organic electroluminescent element |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |