CN113845512A - Compound containing heterocycle and organic electroluminescent device thereof - Google Patents
Compound containing heterocycle and organic electroluminescent device thereof Download PDFInfo
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- CN113845512A CN113845512A CN202111101790.9A CN202111101790A CN113845512A CN 113845512 A CN113845512 A CN 113845512A CN 202111101790 A CN202111101790 A CN 202111101790A CN 113845512 A CN113845512 A CN 113845512A
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Abstract
The invention provides a heterocyclic compound and an organic electroluminescent device thereof, belonging to the technical field of organic electroluminescence. The heterocyclic compound provided by the invention has high electron mobility, can effectively balance carrier transmission in a device, has good hole blocking capability, can effectively block holes in a luminescent layer, avoids transmission of excessive holes to a cathode side, improves the recombination probability of excitons in the luminescent layer, and is applied to a hole blocking/electron transmission layer of an organic electroluminescent device, so that the luminous efficiency of the device is improved, and the service life of the device is prolonged. Meanwhile, the heterocyclic compound has good refractive index, and when the heterocyclic compound is used as a covering layer material, the light-emitting efficiency of the device can be effectively improved, and the light-emitting efficiency of the device is further improved. The heterocyclic compound and the organic electroluminescent device thereof have good application effect and industrialization prospect.
Description
Technical Field
The invention relates to the technical field of organic electroluminescence, in particular to a heterocyclic compound and an organic electroluminescent device thereof.
Background
The Organic Light Emitting Diode (OLED) technology is a technology for converting electric energy into Light energy by using an Organic semiconductor functional material, and has a low operating voltage and a high luminance. It generally comprises a cathode, an organic functional layer and an anode, wherein the organic functional layer essentially comprises: a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an Electron Blocking Layer (EBL), an emission layer (EML), a Hole Blocking Layer (HBL), an Electron Transport Layer (ETL), and an Electron Injection Layer (EIL). In addition, in the top emission device, a high refractive index covering layer is usually disposed outside the semitransparent electrode to adjust the optical interference distance, reduce the total reflection effect of the device, and improve the light extraction efficiency.
Electron transport materials and hole blocking materials are one of the key factors that determine the efficiency and stability of OLED devices. In order to balance the carriers and improve the device efficiency, the electron transport material and the hole blocking material are generally required to have the following characteristics: (1) can be prepared in large batch; (2) has good thermal stability; (3) the material has a lower HOMO energy level, can effectively prevent the transmission of holes, and enables an exciton recombination zone to be formed in the light-emitting layer instead of the electron transmission layer; (4) the material has higher electron mobility, is beneficial to the transmission of electrons, blocks holes, reduces the electron injection barrier and balances carriers; (5) a good amorphous film can be formed, and the performance degradation due to crystallization is avoided. For the covering material, the covering material needs to have higher refractive index in a visible light range, higher glass transition temperature, higher thermal stability, good absorption to an ultraviolet band and avoid the adverse effect of harmful light on device materials; the light-emitting diode does not absorb visible light wave bands, and reduces the influence on the light-emitting efficiency and the color purity of the device.
However, the electron transport materials used at present have low electron mobility and mismatched energy levels, which cause unbalanced carrier injection inside the device and excessive hole transport to the cathode side, thereby causing reduction in the light emitting efficiency of the device and shortening of the service life of the device. In addition, the research on light extraction materials at home and abroad is less, and the performance of most light extraction materials is poorer, so that the light trapped in the device can not be effectively coupled out. Therefore, it is an urgent need to develop an organic electroluminescent material with high electron mobility, which can effectively block holes and improve light extraction efficiency.
Disclosure of Invention
In view of the problems in the prior art, the present invention provides a heterocyclic compound and an organic electroluminescent device thereof, wherein the heterocyclic compound is applied to the organic electroluminescent device as an electron transport/hole blocking layer, and can improve the luminous efficiency of the device and prolong the service life of the device.
The present invention provides a heterocycle-containing compound having a structure represented by chemical formula 1,
in chemical formula 1, Ar is1、Ar2The same or different structures selected from those represented by chemical formula 2
Said Y is the same or different and is selected from C (Rx) or N, wherein at least one Y is selected from N; the Rx is the same or different and is selected from any one of hydrogen, deuterium, cyano, halogen, nitro, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C2-C30 heteroaryl, or two adjacent Rx are connected to form a substituted or unsubstituted ring;
said X1Any one selected from O, S or N (Ry); the above-mentionedRy is any one of hydrogen, deuterium, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C2-C30 heteroaryl;
n is selected from 0,1, 2 or 3;
said E1、E2、E3Independently selected from any one of hydrogen, substituted or unsubstituted benzene ring, substituted or unsubstituted naphthalene ring and substituted or unsubstituted pyridine ring;
the Z is the same or different and is selected from C or N;
said L1～L3The same or different one selected from single bond, substituted or unsubstituted arylene of C6-C30 and substituted or unsubstituted heteroarylene of C2-C30;
the R is1、R2Any one of the same or different hydrogen, deuterium, cyano, halogen, nitro, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C2-C30 heteroaryl; a is a1Selected from 0,1, 2,3, 4,5, 6,7, 8,9, 10 or 11; a is a2Selected from 0,1, 2 or 3.
The invention also provides an organic electroluminescent device which comprises an anode, an organic layer and a cathode, and is characterized in that the organic layer contains any one or the combination of at least two of the compounds containing the heterocyclic ring.
The invention has the beneficial effects that: the heterocyclic compound provided by the invention has high electron mobility, can effectively balance carrier transmission in a device, has good hole blocking capability, can effectively block holes in a luminescent layer, avoids transmission of excessive holes to a cathode side, improves the recombination probability of excitons in the luminescent layer, and is applied to a hole blocking/electron transmission layer of an organic electroluminescent device, so that the luminous efficiency of the device is improved, and the service life of the device is prolonged. Meanwhile, the heterocyclic compound has good refractive index, and when the heterocyclic compound is used as a covering layer material, the light-emitting efficiency of the device can be effectively improved, and the light-emitting efficiency of the device is further improved.
Detailed Description
The following will clearly and completely describe the technical solutions of the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the scope of protection of the present invention.
In the present specification, "-" means a moiety linked to another substituent.
In the present specification, when the position of a substituent on an aromatic ring is not fixed, it means that it can be attached to any of the corresponding optional positions of the aromatic ring. For example,
can represent
And so on.
The halogen in the invention refers to fluorine, chlorine, bromine and iodine.
The alkyl group in the present invention refers to a hydrocarbon group obtained by removing one hydrogen atom from an alkane molecule, and may be a straight-chain alkyl group or a branched-chain alkyl group, preferably having 1 to 30 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 10 carbon atoms, and particularly preferably 1 to 6 carbon atoms, and examples may include a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, a hexyl group, and the like, but are not limited thereto.
The cycloalkyl group in the present invention means a hydrocarbon group obtained by removing one hydrogen atom from a cycloalkane molecule, and preferably has 3 to 15 carbon atoms, more preferably 3 to 10 carbon atoms, and particularly preferably 3 to 6 carbon atoms, and examples thereof may include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, norbornyl, bornyl, and the like. The alkyl group is preferably a cyclopentyl group, a cyclohexyl group, an adamantyl group or a norbornyl group.
The aryl group in the present invention refers to a general term of monovalent group remaining after one hydrogen atom is removed from the aromatic nucleus carbon of the aromatic hydrocarbon molecule, and may be monocyclic aryl group, polycyclic aryl group or condensed ring aryl group, preferably having 6 to 60 carbon atoms, preferably 6 to 18 carbon atoms, more preferably 6 to 14 carbon atoms, most preferably 6 to 12 carbon atoms, and examples may include phenyl group, biphenyl group, terphenyl group, naphthyl group, anthryl group, phenanthryl group, pyrenyl group, triphenylene group, perylenyl group, etc., but are not limited thereto.
The heteroaryl group in the present invention is a general term for a monovalent group obtained by removing a hydrogen atom from a nuclear atom of an aromatic heterocyclic ring composed of carbon and a hetero atom. The hetero atom may be one or more of N, O, S, Si, P, may be a monocyclic heteroaryl group or a fused ring heteroaryl group, preferably having 2 to 60 carbon atoms, preferably 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 3 to 12 carbon atoms, most preferably 3 to 8 carbon atoms, and examples may include a pyrrolyl group, a pyridyl group, a pyrimidinyl group, a triazinyl group, a thienyl group, a furyl group, an indolyl group, a quinolyl group, an isoquinolyl group, an oxazolyl group, a thiazolyl group, an imidazolyl group, a benzothienyl group, a benzofuryl group, a benzoxazolyl group, a benzothiazolyl group, a benzimidazolyl group, a pyridooxazolyl group, a pyridothiazolyl group, a pyridoimidazolyl group, a pyrimidooxazolyl group, a pyrimido thiazolyl group, a pyrimidooimidazolyl group, a dibenzofuryl group, a dibenzothienyl group, a carbazolyl group, a phenazinyl group, a quinoxalinyl group, a quinazolino oxazolyl group, a quinoxalinyl group, a, Quinolinothiazolyl, quinolinoimidazolyl, purinyl, 2-purinyl, N-imidazolyl, and the like, but is not limited thereto.
The arylene group in the present invention refers to a general term of divalent groups remaining after two hydrogen atoms are removed from an aromatic nucleus of an aromatic hydrocarbon molecule, and may be monocyclic arylene group, polycyclic arylene group or condensed ring arylene group, preferably having 6 to 60 carbon atoms, preferably 6 to 25 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 18 carbon atoms, and most preferably 6 to 12 carbon atoms, and examples may include phenylene, biphenylene, terphenylene, naphthylene, anthrylene, phenanthrylene, pyrenylene, triphenylene, peryleneene, and the like, but are not limited thereto.
Heteroarylene as used herein refers to a general term in which two hydrogen atoms are removed from the core carbon of an aromatic heterocyclic ring composed of carbon and hetero atoms, which may be one or more of N, O, S, Si, P, a monocyclic heteroarylene group or a fused-ring heteroarylene group, preferably having 2 to 60 carbon atoms, preferably 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 3 to 12 carbon atoms, most preferably 3 to 8 carbon atoms, and examples may include pyrrolylene, pyridylene, pyrimidylene, triazinylene, thienylene, furylene, indolyl, quinolylene, isoquinolylene, oxazolylene, thiazolyl, imidazolyl, benzothienyl, benzofuranylene, benzoxazylene, benzothiazylene, benzimidazolylene, pyridooxazolylene, pyridothiazolyl, pyridinothiazole, or the like, Pyridinylimidazolylides, pyrimidinyoxazolyl, pyrimidinylthiozolyl, pyrimidinylimidazolylides, dibenzofuranylidene, dibenzothiophenyl, carbazolyl, phenazinylene, quinoxalinyl, quinazolinylene, quinoxalinyl, quinolinoyloxazolylene, quinolinoylthiazole, quinolinoylimidazolyl, purinylene and the like, but are not limited thereto.
The "substitution" as referred to herein means that a hydrogen atom in a compound group is replaced with another atom or group, and the position of substitution is not limited.
The "substituted or unsubstituted" as referred to herein means not substituted or substituted with one or more substituents selected from the group consisting of: deuterium, a halogen atom, amino, cyano, nitro, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C6-C60 aryl group, a substituted or unsubstituted C2-C60 heteroaryl group, a substituted or unsubstituted C6-C60 arylamine group, a substituted or unsubstituted C6-C60 aryloxy group, preferably deuterium, a halogen atom, cyano, a C1-C12 alkyl group, a C6-C30 aryl group, a C2-C30 heteroaryl group, and specific examples thereof may include deuterium, fluorine, chlorine, bromine, iodine, cyano, methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, cyclopropyl, cyclohexyl, adamantyl, norbornanyl,Phenyl, tolyl, mesityl, pentadeuterated phenyl, biphenyl, naphthyl, anthryl, phenanthryl, benzophenanthryl, pyrenyl, triphenylene, and triphenylene,
A group, a perylene group, a fluoranthenyl group, a 9, 9-dimethylfluorenyl group, a 9, 9-diphenylfluorenyl group, a 9-methyl-9-phenylfluorenyl group, a carbazolyl group, a 9-phenylcarbazolyl group, a spirobifluorenyl group, a carbazoloindolyl group, a pyrrolyl group, a furyl group, a thienyl group, an indolyl group, a benzofuryl group, a benzothienyl group, a dibenzofuryl group, a dibenzothienyl group, a pyridyl group, a pyrimidinyl group, a pyridazinyl group, a pyrazinyl group, a triazinyl group, an oxazolyl group, a thiazolyl group, an imidazolyl group, a benzoxazolyl group, a benzothiazolyl group, a benzotriazolyl group, a benzimidazolyl group, a pyridooxazolyl group, a pyridothiazolyl group, a pyridoimidazolyl group, a pyrimidooxazolyl group, a pyrimido thiazolyl group, a pyrimido imidazolyl group, a quinolyl group, an isoquinolyl group, a quinooxazolyl group, a quinolothiazolyl group, a phenothiazinyl group, a phenoxazinyl group, Acridinyl, and the like, but are not limited thereto. Or when the substituent is plural, adjacent substituents may be bonded to form a ring; when the substituent is plural, plural substituents are the same as or different from each other.
The linking to form a substituted or unsubstituted ring according to the present invention means that the two groups are linked to each other by a chemical bond and optionally aromatized. As exemplified below:
in the present invention, the ring formed by the connection may be a five-membered ring or a six-membered ring or a fused ring, and examples may include benzene, pyridine, pyrimidine, naphthalene, cyclopentene, cyclopentane, cyclohexane, cyclohexano, quinoline, isoquinoline, dibenzothiophene, phenanthrene or pyrene, but are not limited thereto.
The present invention provides a heterocycle-containing compound having a structure represented by chemical formula 1,
in chemical formula 1, Ar is1、Ar2The same or different structures selected from those represented by chemical formula 2
Said Y is the same or different and is selected from C (Rx) or N, wherein at least one Y is selected from N; the Rx is the same or different and is selected from any one of hydrogen, deuterium, cyano, halogen, nitro, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C2-C30 heteroaryl, or two adjacent Rx are connected to form a substituted or unsubstituted ring;
said X1Any one selected from O, S or N (Ry); the Ry is selected from any one of hydrogen, deuterium, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C2-C30 heteroaryl;
n is selected from 0,1, 2 or 3;
said E1、E2、E3Independently selected from any one of hydrogen, substituted or unsubstituted benzene ring, substituted or unsubstituted naphthalene ring and substituted or unsubstituted pyridine ring;
the Z is the same or different and is selected from C or N;
said L1～L3The same or different one selected from single bond, substituted or unsubstituted arylene of C6-C30 and substituted or unsubstituted heteroarylene of C2-C30;
the R is1、R2The same or different is selected from hydrogen, deuterium, cyano, halogen, nitro, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C2-C30Any one of the heteroaryl groups of (a); a is a1Selected from 0,1, 2,3, 4,5, 6,7, 8,9, 10 or 11; a is a2Selected from 0,1, 2 or 3.
Preferably, the heterocycle-containing compound is selected from any one of the structures shown below,
preferably, the heterocyclic ring-containing compound is any one selected from the group consisting of structures represented by chemical formulas 1-1 to 6,
the R is1One selected from the group consisting of hydrogen, deuterium, cyano, halogen, methyl, ethyl, isopropyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, norbornyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted triphenylenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidyl, substituted or unsubstituted triazinyl, substituted or unsubstituted oxazolyl, substituted or unsubstituted thiazolyl, substituted or unsubstituted imidazolyl, substituted or unsubstituted furyl, substituted or unsubstituted thienyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted dibenzofuran, and substituted or unsubstituted dibenzothiophene; a is a1Selected from 0,1, 2,3, 4,5, 6,7, 8,9, 10 or 11.
Preferably, the first and second liquid crystal materials are,
at least one Y is selected from N.
Preferably, the first and second liquid crystal materials are,
at least two Y are selected from N, or at least three Y are selected from N, or four Y are all selected from N.
Preferably, the first and second liquid crystal materials are,
at least one Y is selected from N.
Preferably, the first and second liquid crystal materials are,
at least two Y are selected from N, or at least three Y are selected from N, or at least four Y are selected from N.
Preferably, when n is selected from 0,
at least one Y is selected from N.
Preferably, when n is selected from 1,2 or 3,
at least one Y is selected from N.
Preferably, the
Any one selected from the group consisting of,
wherein, R is3Any one of the same or different hydrogen, deuterium, cyano, halogen, nitro, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C2-C30 heteroaryl;
m1selected from 0,1, 2 or 3, m2Independently selected from 0,1 or 2, m3Independently selected from 0 or 1, m4Independently selected from 0,1, 2,3, 4 or 5, m5Independently selected from 0,1, 2,3 or 4, when m1、m2、m4、m5Greater than 1, two or more R3The same or different from each other.
Preferably, the
Any one selected from the group consisting of,
preferably, the
Any one selected from the following groups:
preferably, when n is 0, the above
Selected from those structures in which the six-membered ring fused to the five-membered ring contains an N atom.
Preferably, said L1～L3The same or different is selected from single bond or any one of the following groups:
wherein, R is4Independently selected from hydrogen, deuterium, cyano, substituted or unsubstituted C1 &Any one of C6 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C18 aryl and substituted or unsubstituted C2-C12 heteroaryl;
b is1Independently selected from 0,1, 2,3 or 4, b2Independently selected from 0,1, 2,3, 4,5 or 6, b3Independently selected from 0,1, 2,3, 4,5, 6,7 or 8, b4Independently selected from 0,1, 2 or 3, b5Independently selected from 0,1 or 2, b6Independently selected from 0,1, 2,3, 4 or 5, when b1、b2、b3、b4、b5、b6Greater than 1, two or more R4The same or different from each other.
Preferably, the heterocyclic compound is selected from any one of the following structures:
the invention also provides a preparation method of the compound containing the heterocycle,
E1～E3、L1～L3、R0、R1、R2、X1、Y、Z、n、a1、a2the definitions are the same as above;
the type of reaction involved in the heterocyclic ring-containing compounds of the present invention is the Suzuki reaction.
The present invention may be bonded to the above-mentioned substituents through a method known in the art, and the kind and position of the substituents or the number of the substituents may be changed according to the technique known in the art.
The invention also provides an organic electroluminescent device which comprises an anode, an organic layer and a cathode, wherein the organic layer comprises the compound containing the heterocycle.
The organic layer comprises at least one of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer and a covering layer. However, the structure of the organic electroluminescent device of the present invention is not limited to the above structure, and multiple organic layers may be omitted or simultaneously provided, if necessary. For example, an electron blocking layer may be further provided between the hole transport layer and the light emitting layer, and a hole blocking layer may be further provided between the electron transport layer and the light emitting layer; the organic layers having the same function may be formed in a stacked structure of two or more layers.
The light-emitting layer of the present invention may include a host material, a dopant material, and the like, and may be formed of a single-layer structure or a multilayer structure in which layers above each other are stacked.
The organic electroluminescent device of the present invention preferably has the following structure:
substrate/anode/hole injection layer/hole transport layer/light emitting layer/electron transport layer/electron injection layer/cathode;
substrate/anode/hole injection layer/hole transport layer/light emitting layer/electron transport layer/electron injection layer/cathode/capping layer;
substrate/anode/hole injection layer/hole transport layer/light emitting layer/hole blocking layer/electron transport layer/electron injection layer/cathode;
substrate/anode/hole injection layer/hole transport layer/light emitting layer/hole blocking layer/electron transport layer/electron injection layer/cathode/capping layer;
substrate/anode/hole injection layer/hole transport layer/electron blocking layer/luminescent layer/hole blocking layer/electron transport layer/electron injection layer/cathode;
substrate/anode/hole injection layer/hole transport layer/electron blocking layer/luminescent layer/hole blocking layer/electron transport layer/electron injection layer/cathode/cover layer;
substrate/anode/hole injection layer/hole transport layer/light-emitting auxiliary layer/light-emitting layer/hole blocking layer/electron transport layer/electron injection layer/cathode;
substrate/anode/hole injection layer/hole transport layer/light-emitting auxiliary layer/light-emitting layer/hole blocking layer/electron transport layer/electron injection layer/cathode/cover layer;
however, the structure of the organic electroluminescent device is not limited thereto. The organic electroluminescent device can be selected and combined according to the parameter requirements of the device and the characteristics of materials, part of organic layers can be added or omitted, and the organic layers with the same function can be made into a laminated structure with more than two layers.
The organic electroluminescent device of the present invention is generally formed on a substrate. The substrate may be any substrate as long as it does not change when forming an electrode or an organic layer, for example, a substrate of glass, plastic, a polymer film, silicon, or the like.
In the organic electroluminescent device according to the present invention, it is preferable to use a high work function material capable of promoting hole injection into the organic layer as the anode material. Specific examples of the anode material usable in the present invention may include: metals such as vanadium, chromium, copper, zinc and gold, or alloys thereof; metal oxides such as zinc oxide, Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO); combinations of metals and oxides, such as ITO-Ag-ITO; and conductive polymers such as poly (3-methylthiophene), polypyrrole, polyaniline, poly [3,4- (ethylene-1, 2-dioxy) thiophene ] (PEDT), and the like, but not limited thereto. Preferably, the anode material is selected from ITO, ITO-Ag-ITO and the like.
In the organic electroluminescent device according to the present invention, the hole injection material is preferably a material having a good hole accepting ability. Specific examples of the hole injection material that can be used in the present invention may include: metal oxides such as silver oxide, vanadium oxide, tungsten oxide, copper oxide, titanium oxide, phthalocyanine compound, benzidine compound, phenazine compound, and the like, for example, copper phthalocyanine (CuPc), titanyl phthalocyanine, N, N ' -diphenyl-N, N ' -di- [4- (N, N-diphenylamine) phenyl ] benzidine (NPNPNPNPB), N, N, N ', N ' -tetrakis (4-methoxyphenyl) benzidine (MeO-TPD), bisquinoxalino [2,3-a:2',3' -c ] phenazine (HATNA), 4' -tris [ 2-naphthylphenylamino ] triphenylamine (2T-NATA), 2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-hexaazatriphenylene (HAT-CN), 4,4' -tris (N, N-diphenylamino) triphenylamine (TDATA), and the like, but is not limited thereto. Preferably, the hole injection material of the present invention is selected from copper phthalocyanine (CuPc), 4',4 ″ -tris [ 2-naphthylphenylamino ] triphenylamine (2T-NATA), 4',4 ″ -tris (N, N-diphenylamino) triphenylamine (TDATA), and the like.
In the organic electroluminescent device of the present invention, the hole transport material is preferably a material having an excellent hole transport property and a HOMO level matched with a corresponding anode material. Specific examples of the hole transporting material usable in the present invention may include diphenylamines, triphenylamines, fluorenes and carbazoles, such as N, N ' -diphenyl-N, N ' - (1-naphthyl) -1,1' -biphenyl-4, 4' -diamine (NPB), N ' -di (naphthalen-1-yl) -N, N ' -di (phenyl) -2,2' -dimethylbenzidine (. alpha. -NPD), N ' -diphenyl-N, N ' -di (3-methylphenyl) -1,1' -biphenyl-4, 4' -diamine (TPD), 4- [1- [4- [ di (4-methylphenyl) amino ] phenyl ] cyclohexyl ] -N- (3-methylphenyl) -N- (4-methylphenyl) aniline (TAPC), and the like, but is not limited thereto. Preferably, the hole transport material of the present invention is selected from N, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine (NPB), N '-di (naphthalen-1-yl) -N, N' -di (phenyl) -2,2 '-dimethylbenzidine (α -NPD), 4' -cyclohexyldi [ N, N-di (4-methylphenyl) aniline ] (TAPC), and the like.
In the organic electroluminescent device of the present invention, the light-emitting layer material includes a light-emitting layer host material and a light-emitting layer dopant material, and the light-emitting layer host material may be selected from 4,4 '-bis (9-Carbazole) Biphenyl (CBP), 9, 10-bis (2-naphthyl) Anthracene (ADN), 4-bis (9-carbazolyl) biphenyl (CPB), 9' - (1, 3-phenyl) bis-9H-carbazole (mCP), 4',4 ″ -tris (carbazol-9-yl) triphenylamine (TCTA), 9, 10-bis (1-naphthyl) anthracene (α -ADN), N' -bis- (1-naphthyl) -N, N '-diphenyl- [1,1':4',1": 4', 1' -quaterphenyl.]-4,4' -diamino (4PNPB), 1,3, 5-tris (9-carbazolyl) benzene (TCP), and the like, but is not limited thereto. Preferably, the light-emitting layer host material of the present invention is selected from 9, 10-bis (2-naphthyl) Anthracene (ADN), 9'- (1, 3-phenyl) bis-9H-carbazole (mCP), 4',4 ″ -tris (carbazol-9-yl) triphenylamine (TCTA), 9, 10-bis (1-naphthyl) anthracene (α -AND), AND the like. The luminescent layer doping material can be selected from (6- (4- (diphenylamino (phenyl) -N, N-diphenylpyrene-1-amine) (DPAP-DPPA), 2,5,8, 11-tetra-tert-butylperylene (TBPe), 4' -bis [4- (diphenylamino) styryl]Biphenyl (BDAVBi), 4' -bis [4- (di-p-tolylamino) styryl]Biphenyl (DPAVBi), bis (2-hydroxyphenylpyridine) beryllium (Bepp2), bis (4, 6-difluorophenylpyridine-C2, N) picolinyliridium (FIrpic), tris (2-phenylpyridine) iridium (Ir (ppy)3) Bis (2-phenylpyridine) iridium acetylacetonate (Ir (ppy)2(acac)), 9, 10-bis [ N- (p-tolyl) anilino group]Anthracene (TPA), 4- (dicyanomethylene) -2-methyl-6- (4-dimethylaminostyryl) -4H-pyran (DCM), tris [ 1-phenylisoquinoline-C2, N]Iridium (III) (Ir (piq)3) Bis (1-phenylisoquinoline) (acetylacetonato) iridium (Ir (piq))2(acac)), etc., but is not limited thereto. Preferably, the light emitting layer guest of the present invention is selected from 4,4' -bis [4- (di-p-tolylamino) styryl]Biphenyl (DPAVBi), 2,5,8, 11-tetra-tert-butylperylene (TBPe), 9, 10-di [ N- (p-tolyl) anilino group]Anthracene (TPA), 4- (dicyanomethylene) -2-methyl-6- (4-dimethylaminostyryl) -4H-pyran (DCM), and the like.
The doping ratio of the host material for the light-emitting layer and the dopant material for the light-emitting layer is preferably different depending on the materials used, and is usually 0.01% to 20%, preferably 0.1% to 15%, more preferably 1% to 10%.
In the organic electroluminescent device according to the present invention, the hole blocking material has a strong hole blocking ability and suitable HOMO and LUMO energy levels, and specific examples of the hole blocking material that may be used in the present invention may include imidazoles, triazoles, phenanthroline derivatives, quinolines, and the like, such as 2,9- (dimethyl) -4, 7-biphenyl-1, 10-phenanthroline (BCP), 1,3, 5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene (TPBi), 4, 7-diphenyl-1, 10-phenanthroline (Bphen), and the like, in addition to the heterocyclic ring-containing compound according to the present invention, but are not limited thereto. Preferably, the hole blocking material of the present invention is selected from the heterocyclic ring-containing compounds of the present invention.
In the organic electroluminescent device according to the present invention, the electron transport material is preferably a material having a strong electron withdrawing ability and low HOMO and LUMO energy levels, and specific examples of the electron transport material that may be used in the present invention, in addition to the heterocyclic ring-containing compound according to the present invention, may include imidazoles, triazoles, phenanthroline derivatives, quinolines, and the like, such as 2,9- (dimethyl) -4, 7-biphenyl-1, 10-phenanthroline (BCP), 1,3, 5-tris [ (3-pyridyl) -phenyl ] phenanthrene (BCP)]Benzene (TmPyPB), 4' -bis (4, 6-diphenyl-1, 3, 5-triazinyl) biphenyl (BTB), 1,3, 5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene (TPBi), 3- (biphenyl-4-yl) -5- (4-tert-butylphenyl) -4-phenyl-4H-1, 2, 4-Triazole (TAZ), 2- (naphthalen-2-yl) -4,7- (diphenyl) -1, 10-phenanthroline (HNBphen), 8-hydroxyquinoline-Lithium (LiQ), and the like, but are not limited thereto. Preferably, the electron transport material of the present invention is selected from 1,3, 5-tris (N-phenyl-2-benzimidazole) benzene (TPBi), tris (8-hydroxyquinoline) aluminum (III) (Alq)3) 8-hydroxyquinoline-lithium (Liq), bis (2-methyl-8-hydroxyquinoline) (4-phenylphenol) aluminum (III) (BAlq), and the like, but not limited thereto, it is preferable that the electron transport material of the present invention is selected from the heterocyclic ring-containing compounds of the present invention.
In the organic electroluminescent device of the present invention, the electron injection material is preferably a material having a small difference in potential barrier with an adjacent organic transport material or host material, and the like, and hasThe effect of injecting electrons from the cathode. Examples of the electron injecting material that can be used in the present invention include: alkali metal salts (such as LiF, CsF), alkaline earth metal salts (such as MgF)2) Metal oxides (e.g. Al)2O3、MoO3) But is not limited thereto. Preferably, the electron injection material of the present invention is selected from lithium fluoride (LiF), 8-hydroxyquinoline-lithium (Liq), and the like.
In the organic electroluminescent device according to the present invention, a low work function material capable of promoting electron injection into the organic layer is preferably used as the cathode material. Specific examples of the cathode material that can be used in the present invention may include: metals such as aluminum, magnesium, silver, indium, tin, titanium, and the like, and alloys thereof; multilayer metallic materials, e.g. LiF/Al, Mg/Ag, Li/Al, LiO2/Al、BaF2Al, etc., but are not limited thereto. Preferably, the cathode of the present invention is selected from Ag, Mg — Ag alloy or thin Al.
In the organic electroluminescent device according to the present invention, a material for improving optical coupling is preferably used as the material for the cover layer. Specific examples of the cover layer material that can be used in the present invention may include, but are not limited to, arylamine derivatives, carbazole derivatives, benzimidazole derivatives, triazole derivatives, lithium fluoride, and the like, in addition to the heterocyclic ring-containing compounds described in the present invention, and preferably, the cover layer material described in the present invention is selected from the heterocyclic ring-containing compounds described in the present invention. The coating layer may be formed on both the outer side of the anode and the outer side of the cathode, or may be disposed on the outer side of the anode or the outer side of the cathode, and preferably, the coating layer according to the present invention is disposed on the outer side of the cathode.
The present invention is not particularly limited to the thickness of each organic layer of the organic electroluminescent device, and may be any thickness commonly used in the art.
The organic electroluminescent device of the present invention may employ any one of vacuum evaporation, spin coating, vapor deposition, knife coating, laser thermal transfer, electrospray coating, slit coating, and dip coating, and in the present invention, vacuum evaporation is preferably employed.
The organic electroluminescent device can be widely applied to the fields of panel display, lighting sources, flexible OLEDs, electronic paper, organic solar cells, organic photoreceptors or organic thin film transistors, signs, signal lamps and the like.
The invention is explained in more detail by the following examples, without wishing to restrict the invention accordingly. Based on this description, one of ordinary skill in the art will be able to practice the invention and prepare other compounds and devices according to the invention within the full scope of the disclosure without undue inventive effort.
Preparation and characterization of the Compounds
Description of raw materials, reagents and characterization equipment:
the present invention is not particularly limited to the starting materials and sources of reagents used in the following examples, and they may be commercially available products or prepared by methods known to those skilled in the art.
The mass spectrum uses British Watts G2-Si quadrupole rod series time-of-flight high resolution mass spectrometer, chloroform is used as solvent;
the element analysis uses a Vario EL cube type organic element analyzer of Germany Elementar company, and the mass of a sample is 5-10 mg;
synthesis example 1 Synthesis of intermediate d-1
Preparation of intermediate b-1
Under a nitrogen atmosphere, starting materials a-1(124.80mmol, 24.02g), B2Pin2(137.28mmol，34.86g)，K2CO3(374.40mmol，51.75g)，Pd(PPh3)4(2.50mmol, 2.89g) was added to DMF (600mL), stirred and heated to reflux temperature and reacted for 4 h. After the reaction was completed, it was cooled to room temperature and 900mL of water was added, followed by extraction with dichloromethane, and the organic layer was extracted with anhydrous MgSO4Drying, concentration and recrystallization from ethyl acetate gave intermediate b-1(26.00g, 87% yield); HPLC purity is more than or equal to 98.78%. Mass spectrum m/z: 239.0896 (theoretical value: 239.0884).
Preparation of intermediate d-1
Under a nitrogen atmosphere, intermediate b-1(99.05mmol, 23.72g), raw material c-1(97.11mmol, 19.23g), Pd (PPh) were charged in a reaction flask3)4(1.94mmol，2.24g)、K2CO3(194.22mmol, 26.84g) and 300mL of toluene, 150mL of ethanol, 150mL of water, stirring the mixture, and reacting for 3h under reflux; after the reaction is finished, cooling to room temperature, performing suction filtration to obtain a filter cake, and reacting the filter cake with toluene/ethanol (5: 1 recrystallization to give intermediate d-1(18.59g, 83% yield); HPLC purity is more than or equal to 98.97 percent. Mass spectrum m/z: 230.0258 (theoretical value: 230.0247). Theoretical element content (%) C12H7ClN2O: c, 62.49; h, 3.06; and N, 12.15. Measured elemental content (%): c, 62.44; h, 3.05; and N, 12.17.
Intermediates d-15 to d-542 were prepared according to the preparation of synthesis example 1, with corresponding substitution of the starting materials as shown in the following table:
[ Synthesis example 2] Synthesis of intermediate h-1
Preparation of intermediate g-1
Under a nitrogen atmosphere, a reaction flask was charged with the starting material e-1(104.24mmol, 25.86g), the starting material f-1(102.20mmol, 23.09g), and Pd (PPh)3)4(2.04mmol，2.36g)，K2CO3(204.40mmol, 28.25g) and 300mL toluene, 150mL ethanol, 150mL water, stirring the mixture, under reflux conditions for 3 h; after the reaction is finished, cooling to room temperature, carrying out suction filtration to obtain a filter cake, washing the filter cake with ethanol, and finally, using toluene to wash the filter cakeEthanol ═ 4: 1 recrystallization to give intermediate g-1(31.41g, 88% yield); HPLC purity is more than or equal to 98.86%. Mass spectrum m/z: 348.0481 (theoretical value: 348.0473).
Preparation of intermediate h-1
Under a nitrogen atmosphere, intermediate g-1(82.00mmol, 28.64g), B2Pin2(180.4mmol，45.81g)，KOAc(246mmol，24.14g)，Pd(dppf)Cl2(2.46mmol, 1.80g) was added to DMF (400mL), stirred and heated to reflux temperature and reacted for 4 h. After the reaction was completed, it was cooled to room temperature and 900mL of water was added, followed by extraction with dichloromethane, and the organic layer was extracted with anhydrous MgSO4Drying, concentration, and recrystallization from ethyl acetate afforded intermediate h-1(34.05g, 78% yield); the HPLC purity is more than or equal to 99.04 percent. Mass spectrum m/z: 532.2948 (theoretical value: 532.2956). Theoretical element content (%) C34H38B2O4: c, 76.72; h, 7.20. Measured elemental content (%): c, 76.67; h, 7.23.
Intermediates h-15 to h-526 can be prepared according to the preparation method of synthesis example 2 by replacing the raw materials correspondingly, which are shown in the following table:
[ Synthesis example 3] Synthesis of intermediate h' -1
Preparation of intermediate k-1
A reaction flask was charged with the starting material i-1(92.20mmol, 19.74g), the starting material j-1(94.04mmol, 14.71g), and Pd (PPh) under a nitrogen atmosphere3)4(1.84mmol，2.13g)，K2CO3(184.40mmol, 25.49g) and 300mL of toluene, 150mL of ethanol, 150mL of water, stirring the mixture, and reacting for 3h under reflux; after the reaction was completed, the reaction mixture was cooled to room temperature, filtered to obtain a filter cake, the filter cake was washed with ethanol, and finally recrystallized from toluene/ethanol 5:1 to obtain intermediate k-1(19.94g, yield 88%) (ii) a HPLC purity is more than or equal to 98.89%. Mass spectrum m/z: 245.0997 (theoretical value: 245.0989).
Preparation of intermediate e' -1
Intermediate k-1(75mmol, 18.43g), B2Pin2(82.50mmol, 20.95g), KOAc (225mmol, 22.08g) were dissolved in anhydrous dioxane (840mL), and after nitrogen substitution, Pd (dppf) Cl was added2(1.80mmol, 1.32g) was heated under reflux for 3 hours. After the reaction was completed, it was cooled to room temperature and 900mL of water was added, followed by extraction with dichloromethane, and the organic layer was extracted with anhydrous MgSO4Drying, concentration and recrystallization from ethyl acetate gave intermediate e' -1(21.50g, 85% yield); the HPLC purity is more than or equal to 99.11 percent. Mass spectrum m/z: 337.2220 (theoretical value: 337.2230).
Preparation of intermediate g' -1:
to a reaction flask, under a nitrogen atmosphere, were added the raw material e' -1(60mmol, 20.24g), the raw material f-1(58.82mmol, 13.29g), Pd (dppf) Cl2(1.18mmol, 0.86g), KOAc (117.64mmol, 11.55g) and 180mL toluene, 90mL ethanol, 90mL water, stirring the mixture and reacting under reflux for 4 h; after the reaction is finished, cooling to room temperature, performing suction filtration to obtain a filter cake, washing the filter cake with ethanol, and finally, adding toluene/ethanol (20: 3 recrystallization to give intermediate g' -1(16.98g, 81% yield); the HPLC purity is more than or equal to 99.24 percent. Mass spectrum m/z: 355.0923 (theoretical value: 355.0912).
Preparation of intermediate h' -1
Under a nitrogen atmosphere, intermediates g' -1(45mmol, 16.03g), B2Pin2(99mmol，25.14g)，KOAc(135mmol，13.25g)，Pd(dppf)Cl2(1.35mmol, 0.99g) was added to DMF (220mL), stirred and heated to reflux temperature and reacted for 5 h. After the reaction was completed, it was cooled to room temperature and 900mL of water was added, followed by extraction with dichloromethane, and the organic layer was extracted with anhydrous MgSO4Drying, concentration and recrystallization from ethyl acetate gave intermediate h' -1(18.93g, 78% yield); the HPLC purity is more than or equal to 99.48 percent. Mass spectrum m/z: 539.3385 (theoretical value: 539.3396). Theoretical element content (%) C34H31D7B2O4: c, 75.72; h, 8.41. Measured elemental content (%): c, 75.76; h, 8.42.
Intermediates h '-23 to h' -542 were prepared according to the preparation method of synthesis example 3, with the corresponding substitution of the starting materials as shown in the following table:
synthesis example 4 Synthesis of Compound 1
Preparation of Compound 1
Under nitrogen protection, intermediate h-1(30mmol, 15.97g), intermediate d-1(61.20mmol, 14.12g), Pd were added to a reaction flask2(dba)3(0.30mmol，0.27g)，P(t-Bu)3(2.40mmol, 2.4mL of a 1.0mol/L solution in toluene), K2CO3(60mmol, 8.29g), THF (300mL), stirring the mixture, reacting under reflux for 4.5 h; after the reaction is finished, cooling to room temperature, performing suction filtration to obtain a filter cake, washing the filter cake with ethanol, and finally, adding toluene/ethanol (10: 1 recrystallization to give compound 1(13.84g, 69% yield); the HPLC purity is more than or equal to 99.77 percent. Mass spectrum m/z: 668.2223 (theoretical value: 668.2212). Theoretical element content (%) C46H28N4O2: c, 82.62; h, 4.22; and N, 8.38. Measured elemental content (%): c, 82.57; h, 4.24; n, 8.39.
Compounds 10 to 542 were prepared according to the procedure for the preparation of synthetic example 4, with corresponding substitution of intermediates as shown in the following table:
device examples 1 to 20
The ITO glass substrate is ultrasonically cleaned for 2 times and 20 minutes each time by 5% glass cleaning solution, and then ultrasonically cleaned for 2 times and 10 minutes each time by deionized water. Ultrasonic cleaning with acetone and isopropanol for 20 min, and oven drying at 120 deg.C. Vacuum evaporating HI-1 on an ITO glass substrate to form a hole injection layer, wherein the evaporation thickness is 10 nm; evaporating HT-1 on the hole injection layer in vacuum to form a hole transmission layer, wherein the evaporation thickness is 40 nm; vacuum evaporating RH: RD: 97:3 on the hole transport layer to form a light emitting layer, wherein the evaporation thickness is 25 nm; the compound 15 of the invention is vacuum evaporated on the luminescent layer to be used as an electron transport layer, and the evaporation thickness is 30 nm; evaporating LiF on the electron transport layer in vacuum to form an electron injection layer, wherein the evaporation thickness is 0.5 nm; al was vacuum-deposited on the electron injection layer as a cathode, and the deposition thickness was 70 nm.
Device examples 2 to 16: an organic electroluminescent device was produced by using the same procedure as in device example 1 except that the compound 15 of the present invention in device example 1 was replaced with the compounds 73, 74, 107, 140, 184, 213, 233, 260, 392, 418, 446, 481, 504, 515, 542 of the present invention as an electron transporting material, respectively.
Comparative examples 1 to 5: an organic electroluminescent device was produced by using the same procedure as in device example 1 except that the compound 15 of the present invention in device example 1 was replaced with the compound 1, the compound 2, the compound 3, the compound 4 and the compound 5, respectively, as an electron transport layer.
The test software, computer, K2400 digital source meter manufactured by Keithley corporation, usa, and PR788 spectral scanning luminance meter manufactured by Photo Research corporation, usa were combined into a combined IVL test system to test the luminous efficiency of the organic electroluminescent device. The lifetime was measured using the M6000 OLED lifetime test system from McScience. The environment of the test is atmospheric environment, and the temperature is room temperature. The results of the light emission characteristic test of the obtained organic electroluminescent device are shown in table 1. Table 1 shows the results of the test of the light emitting characteristics of the organic electroluminescent devices prepared from the compounds prepared in the inventive examples and the comparative materials.
Table 1 test of light emitting characteristics of organic electroluminescent device
T97 represents the time required for the luminance of the device to drop to 97% of the initial luminance at constant current density.
As can be seen from the results of table 1, the organic electroluminescent device of the present invention exhibited advantages of high luminous efficiency and long life span, as compared to comparative examples 1 to 5.
Device examples 17 to 39
The ITO glass substrate is ultrasonically cleaned for 2 times and 20 minutes each time by 5% glass cleaning solution, and then ultrasonically cleaned for 2 times and 10 minutes each time by deionized water. Ultrasonic cleaning with acetone and isopropanol for 20 min, and oven drying at 120 deg.C. Vacuum evaporating HI-1 on an ITO glass substrate to form a hole injection layer, wherein the evaporation thickness is 10 nm; evaporating HT-1 on the hole injection layer in vacuum to form a hole transmission layer, wherein the evaporation thickness is 40 nm; vacuum evaporating RH: RD: 97:3 on the hole transport layer to form a light emitting layer, wherein the evaporation thickness is 25 nm; the compound 10 of the invention is vacuum evaporated on the luminescent layer to be used as a hole blocking layer, and the evaporation thickness is 12 nm; evaporating ET-1 on the hole blocking layer in vacuum to form an electron transport layer with the evaporation thickness of 20nm, and evaporating LiF on the electron transport layer in vacuum to form an electron injection layer with the evaporation thickness of 0.5 nm; al was vacuum-deposited on the electron injection layer as a cathode, and the deposition thickness was 70 nm.
Device examples 2 to 39: an organic electroluminescent device was produced by using the same procedure as in device example 17 except that the inventive compound 10 in device example 17 was replaced with the inventive compound 23, 64, 66, 128, 210, 246, 342, 354, 423, 426, 461, 488, 504, 511, 515, respectively, as a hole blocking material.
Comparative examples 6 to 10: an organic electroluminescent device was produced by using the same procedure as in device example 17 except that compound 10 of the present invention in device example 17 was replaced with compound 1, compound 2, compound 3, compound 4 and compound 5, respectively, as a hole-blocking material.
The test software, computer, K2400 digital source meter manufactured by Keithley corporation, usa, and PR788 spectral scanning luminance meter manufactured by Photo Research corporation, usa were combined into a combined IVL test system to test the luminous efficiency of the organic electroluminescent device. The lifetime was measured using the M6000 OLED lifetime test system from McScience. The environment of the test is atmospheric environment, and the temperature is room temperature. The results of the light emission characteristic test of the obtained organic electroluminescent device are shown in table 2. Table 2 shows the results of the test of the light emitting characteristics of the organic electroluminescent devices prepared by the compounds prepared in the inventive examples and the comparative materials.
Table 2 test of light emitting characteristics of organic electroluminescent device
As can be seen from the results of table 2, the organic electroluminescent devices according to the present invention exhibited advantages of high luminous efficiency and long life span, as compared to comparative examples 6 to 10.
Device examples 33 to 41
The glass substrate was ultrasonically cleaned by 5% glass cleaning solution for 2 times, each for 20 minutes, and then ultrasonically cleaned by deionized water for 2 times, each for 10 minutes. Ultrasonic cleaning with acetone and isopropanol for 20 min, and oven drying at 120 deg.C. ITO/Ag/ITO is used as an anode on the glass substrate; vacuum evaporating HI-1 on the anode to form a hole injection layer with the thickness of 10 nm; evaporating HT-1 on the hole injection layer in vacuum to form a hole transmission layer, wherein the evaporation thickness is 40 nm; vacuum evaporating RH: RD: 97:3 on the hole transport layer to form a light emitting layer, wherein the evaporation thickness is 25 nm; vacuum evaporating ET-1 on the light-emitting layer to form an electron transport layer, wherein the evaporation thickness is 30 nm; evaporating LiF on the electron transport layer in vacuum to form an electron injection layer, wherein the evaporation thickness is 0.5 nm; vacuum evaporation of Mg on the electron injection layer: ag 1:9 as a cathode, and the thickness was 20 nm. The compound 1 of the invention is evaporated on the cathode in vacuum as a covering layer material, and the evaporation thickness is 70 nm.
Device examples 34 to 41: an organic electroluminescent device was produced by using the same procedure as in device example 33 except that compound 1 of the present invention in device example 33 was replaced with compound 21, 23, 66, 140, 210, 334, 511, 526 of the present invention as a capping layer material, respectively.
Comparative examples 11 to 12: an organic electroluminescent device was produced by using the same procedure as in device example 33 except that compound 4 and compound 5 of the present invention were used as a capping layer material instead of compound 1 of the present invention in device example 33.
The test software, computer, K2400 digital source meter manufactured by Keithley corporation, usa, and PR788 spectral scanning luminance meter manufactured by Photo Research corporation, usa were combined into a combined IVL test system to test the luminous efficiency of the organic electroluminescent device. The environment of the test is atmospheric environment, and the temperature is room temperature. The results of the light emission characteristic test of the obtained organic electroluminescent device are shown in table 3. Table 3 shows the results of the test of the light emitting characteristics of the organic electroluminescent devices prepared by the compounds prepared in the inventive examples and the comparative materials.
Table 3 test of light emitting characteristics of organic electroluminescent device
As can be seen from the results in Table 3, the organic electroluminescent element of the present invention has an advantage of higher luminous efficiency than those of comparative examples 11 to 12.
It should be understood that the present invention has been particularly described with reference to particular embodiments thereof, but that various changes in form and details may be made therein by those skilled in the art without departing from the principles of the invention and, therefore, within the scope of the invention.
Claims (10)
1. A heterocycle-containing compound, wherein the heterocycle-containing compound has a structure represented by chemical formula 1,
in chemical formula 1, Ar is1、Ar2The same or different structures selected from those represented by chemical formula 2
Said Y is the same or different and is selected from C (Rx) or N, wherein at least one Y is selected from N; the Rx is the same or different and is selected from any one of hydrogen, deuterium, cyano, halogen, nitro, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C2-C30 heteroaryl, or two adjacent Rx are connected to form a substituted or unsubstituted ring;
said X1Any one selected from O, S or N (Ry); the Ry is selected from any one of hydrogen, deuterium, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C2-C30 heteroaryl;
n is selected from 0,1, 2 or 3; when n is greater than 1, a plurality of
Are the same or different from each other;
said E1、E2、E3Independently selected from any one of hydrogen, substituted or unsubstituted benzene ring, substituted or unsubstituted naphthalene ring and substituted or unsubstituted pyridine ring;
the Z is the same or different and is selected from C or N;
said L1～L3The same or different one selected from single bond, substituted or unsubstituted arylene of C6-C30 and substituted or unsubstituted heteroarylene of C2-C30;
the R is1、R2Any one of the same or different hydrogen, deuterium, cyano, halogen, nitro, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C2-C30 heteroaryl; a is a1Selected from 0,1, 2,3, 4,5, 6,7, 8,9, 10 or 11; a is a2Selected from 0,1, 2 or 3.
2. The heterocyclic ring-containing compound according to claim 1, which is characterized in that the heterocyclic ring-containing compound is any one selected from the group consisting of structures represented by chemical formulas 1-1 to 1-6,
the R is1One selected from the group consisting of hydrogen, deuterium, cyano, halogen, methyl, ethyl, isopropyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, norbornyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted triphenylenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidyl, substituted or unsubstituted triazinyl, substituted or unsubstituted oxazolyl, substituted or unsubstituted thiazolyl, substituted or unsubstituted imidazolyl, substituted or unsubstituted furyl, substituted or unsubstituted thienyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted dibenzofuran, and substituted or unsubstituted dibenzothiophene; a is a1Selected from 0,1, 2,3, 4,5, 6,7, 8,9, 10 or 11.
3. A heterocycle-containing compound according to claim 1, wherein said compound is
Any one selected from the group consisting of,
wherein, R is3The same or different is selected from hydrogen, deuterium, cyano, halogen, nitro, substituted or unsubstituted C1-C12 alkyl, substitutedOr any one of unsubstituted C3-C12 naphthenic base, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C2-C30 heteroaryl;
m1selected from 0,1, 2 or 3, m2Independently selected from 0,1 or 2, m3Independently selected from 0 or 1, m4Independently selected from 0,1, 2,3, 4 or 5, m5Independently selected from 0,1, 2,3 or 4, when m1、m2、m4、m5Greater than 1, two or more R3The same or different from each other.
4. A heterocycle-containing compound according to claim 1, wherein said compound is
Any one selected from the group consisting of,
5. a heterocycle-containing compound according to claim 1, wherein said compound is
Any one selected from the following groups:
6. the heterocycle-containing compound of claim 1, wherein L is1～L3The same or different is selected from single bond or any one of the following groups:
wherein, R is4Independently selected from any one of hydrogen, deuterium, cyano, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C18 aryl and substituted or unsubstituted C2-C12 heteroaryl;
b is1Independently selected from 0,1, 2,3 or 4, b2Independently selected from 0,1, 2,3, 4,5 or 6, b3Independently selected from 0,1, 2,3, 4,5, 6,7 or 8, b4Independently selected from 0,1, 2 or 3, b5Independently selected from 0,1 or 2, b6Independently selected from 0,1, 2,3, 4 or 5, when b1、b2、b3、b4、b5、b6Greater than 1, two or more R4The same or different from each other.
7. A heterocycle-containing compound according to claim 1 wherein said heterocycle is selected from any one of the following structures:
8. an organic electroluminescent device comprising an anode, a cathode, and an organic layer, wherein the organic layer comprises at least one heterocyclic ring-containing compound according to any one of claims 1 to 7.
9. An organic electroluminescent device according to claim 8, wherein the organic layer is located between the anode and the cathode, and the organic layer comprises at least one of an electron transport layer or a hole blocking layer, and the electron transport layer or the hole blocking layer comprises at least one of the heterocyclic ring-containing compounds according to claims 1 to 7.
10. An organic electroluminescent device according to claim 8, wherein the organic layer is located outside the cathode, and the organic layer comprises a covering layer, and the covering layer comprises at least one of the heterocyclic ring-containing compounds according to any one of claims 1 to 7.
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