CN109705100B - Naphthalenecarbazole-containing organic photochemical compound, mixture, composition and application thereof - Google Patents

Abstract

The invention relates to a naphthaline carbazole-containing organic compound, a mixture, a composition and application thereof, wherein the naphthaline carbazole-containing organic compound has a structure shown as a structural formula (1-1) or a structural formula (1-2):

Description

Naphthalenecarbazole-containing organic photochemical compound, mixture, composition and application thereof

The present application claims priority of chinese patent application entitled "a naphthalene carbazole-containing organic photoelectric material and use thereof" filed by the chinese patent office on 22.12/2017 and having an application number of 201711406898.2, which is incorporated herein by reference in its entirety.

Technical Field

The invention relates to the field of electroluminescent materials, in particular to naphthaline carbazole-containing organic photochemical compounds, mixtures, compositions and application thereof.

Background

The organic photoelectric material has diversity in synthesis, relatively low manufacturing cost and excellent optical and electrical properties. Organic Light Emitting Diodes (OLEDs) have the advantages of wide viewing angle, fast response time, low operating voltage, thin panel thickness, etc., in the application of optoelectronic devices, such as flat panel displays and lighting, and thus have a wide potential for development.

In order to improve the light emitting efficiency of the organic light emitting diode, various light emitting material systems based on fluorescence and phosphorescence have been developed, and the organic light emitting diode using a fluorescent material has a high reliability but is limited in its internal electroluminescence quantum efficiency to 25% under electrical excitation because the branching ratio of the singlet excited state and the triplet excited state of excitons is 1: 3. In contrast, the organic light emitting diode using the phosphorescent material has achieved almost 100% internal electroluminescence quantum efficiency. Theoretically, the luminous efficiency of phosphorescent materials can be increased to 4 times compared to fluorescent materials, and thus the development of phosphorescent materials has been widely studied.

The light emitting material (guest) may be used as a light emitting material together with a host material (host) to improve color purity, light emitting efficiency, and stability. Since the host material greatly affects the efficiency and characteristics of the electroluminescent device when the host material/guest system is used as the light emitting layer of the light emitting device, the selection of the host material is important.

Currently, 4, 4' -dicarbazole-biphenyl (CBP) is known to be the most widely used as a host material for phosphorescent substances. In recent years, Pioneer corporation (Pioneer) and the like have developed a high-performance organic electroluminescent device using a compound such as BAlq (bis (2-methyl) -8-hydroxyquinolinato-4-phenylphenolaluminum (III)), phenanthroline (BCP), and the like as a substrate.

In the prior art material designs, one tends to use a composition containing an electron transport group and a hole transport group, designed as a host of bipolar transport, beneficial to the balance of charge transport, as described in patents US2016329506, US20170170409, etc., or as a class of triazine or pyrimidine derivatives disclosed in patent CN 104541576A. The bipolar transmission molecules are used as main bodies, so that good device performance can be obtained. The performance and lifetime of the resulting devices remain to be improved.

Thus, there is a need for improvements and developments in the art, particularly in the host material solutions.

Disclosure of Invention

Based on the above, there is a need to provide a naphthaline carbazole-containing organic photochemical compound, a mixture, a composition and a use thereof, which can solve the problems of high cost, fast efficiency roll-off under high brightness and short service life of the existing phosphorescent light-emitting material, and solve the problems of low light-emitting efficiency and short service life of the TADF organic light-emitting material.

The technical scheme of the invention is as follows:

a naphthalocarbazole-containing organic compound has a structure shown as a structural formula (1-1) or a structural formula (1-2):

wherein:

Ar₁、Ar₂each independently selected from substituted or unsubstituted aryl or heteroaryl groups having from 5 to 30 ring atoms, or from substituted or unsubstituted aryl or heteroaryl groups having from 5 to 30 ring atomsA non-aromatic ring group of ring atoms;

the naphthalene carbazole-containing organic compound may be further substituted with a substituent R₁Substitution;

R₁、R₂each independently selected from H, D, straight chain alkyl having 1 to 20C atoms, alkoxy having 1 to 20C atoms, thioalkoxy having 1 to 20C atoms, branched or cyclic alkyl having 3 to 20C atoms, branched or cyclic alkoxy having 3 to 20C atoms, branched or cyclic thioalkoxy having 3 to 20C atoms, silyl, keto having 1 to 20C atoms, alkoxycarbonyl having 2 to 20C atoms, aryloxycarbonyl having 7 to 20C atoms, cyano, carbamoyl, haloformyl, formyl, isocyano, isocyanato, thiocyanate, isothiocyanate, hydroxyl, nitro, CF, and mixtures thereof₃Cl, Br, F, a crosslinkable group, a substituted or unsubstituted aromatic or heteroaromatic group having 5 to 30 ring atoms, an aryloxy or heteroaryloxy group having 5 to 30 ring atoms;

a is 1,2,3 or 4;

b is 1,2,3,4, 5 or 6;

when there are more than one R₁When a plurality of R₁Are the same or different from each other; when there are more than one R₂When a plurality of R₂Are the same or different from each other;

each Z₁Independently selected from CR₃Or N, at least one Z₁Is N; r₃Is as defined for R₁And R₂。

The naphthalene carbazole-containing high polymer has a structure in which the repeating unit of the naphthalene carbazole-containing high polymer contains the organic compound.

A naphthalene carbazole-containing mixture, which comprises the naphthalene carbazole-containing organic compound or the naphthalene carbazole-containing high polymer and at least one organic functional material; the organic functional material is a hole injection material, a hole transport material, an electron injection material, an electron blocking material, a hole blocking material, a light-emitting body or a host material.

A naphthaline carbazole-containing composition, which comprises the naphthaline carbazole-containing organic compound or the naphthaline carbazole-containing high polymer and at least one organic solvent.

The application of the organic compound containing the naphthaline carbazole, the high polymer containing the naphthaline carbazole and the mixture containing the naphthaline carbazole in organic electronic devices.

An organic electronic device at least comprises one of the organic compound containing the naphthazole, the high polymer containing the naphthazole and the mixture containing the naphthazole.

An organic electronic device comprising a light-emitting layer containing one or more of the above-mentioned naphthalene carbazole-containing organic compound, the above-mentioned naphthalene carbazole-containing high polymer, and the above-mentioned naphthalene carbazole-containing mixture.

The organic compound containing the naphthaline carbazole, the high polymer containing the naphthaline carbazole and the mixture containing the naphthaline carbazole can be used as a host material, and the luminescent efficiency and the service life of the electroluminescent device can be improved by matching with a proper object, particularly a phosphorescent object or a TADF (TADF) luminophor, so that a solution of the luminescent device with low manufacturing cost, high efficiency, long service life and low roll-off is provided. In addition, the organic electroluminescent device is matched with another body with hole transport property or bipolar property to form a common body, so that the electroluminescent efficiency and the service life of the device can be further improved.

Detailed Description

The present invention provides a naphthocarbazole-containing organic photochemical compound, a mixture, a composition and a use thereof, and the present invention is further described in detail below in order to make the objects, technical schemes and effects of the present invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

In the present invention, "D" and "deuterium atom" in the substituent have the same meaning, and they may be interchanged with each other.

In the present invention, the composition and the printing ink, or ink, have the same meaning and are interchangeable.

In the present invention, the Host material, Matrix material, Host or Matrix material have the same meaning and are interchangeable with each other.

In the present invention, HOMO represents the highest occupied molecular orbital and LUMO represents the lowest unoccupied molecular orbital.

In the present invention, the triplet energy level may be nominally E_T1，T1，T₁They have the same meaning.

In the present invention, "substituted" means that a hydrogen atom in a substituent is substituted by a substituent.

In the present invention, the "number of ring atoms" represents the number of atoms among atoms constituting the ring itself of a structural compound (for example, a monocyclic compound, a condensed ring compound, a crosslinked compound, a carbocyclic compound, and a heterocyclic compound) in which atoms are bonded in a ring shape. When the ring is substituted with a substituent, the atoms contained in the substituent are not included in the ring-forming atoms. The "number of ring atoms" described below is the same unless otherwise specified. For example, the number of ring atoms of the benzene ring is 6, the number of ring atoms of the naphthalene ring is 10, and the number of ring atoms of the thienyl group is 5.

In the embodiment of the present invention, the energy level structure of the organic material, the triplet state energy level E_T1HOMO, LUMO play a key role. The determination of these energy levels is described below.

The HOMO and LUMO energy levels can be measured by the photoelectric effect, for example XPS (X-ray photoelectron spectroscopy) and UPS (ultraviolet photoelectron spectroscopy) or by cyclic voltammetry (hereinafter referred to as CV). Recently, quantum chemical methods, such as the density functional theory (hereinafter abbreviated as DFT), have become effective methods for calculating the molecular orbital level.

Triplet energy level E of organic material_T1Can be measured by low temperature Time resolved luminescence spectroscopy, or can be obtained by quantum simulation calculations (e.g., by Time-dependent DFT), such as by commercial software Gaussian 03W (Gaussian Inc.), specific simulation methods can be found in WO2011141110 or as described in the examples below.

Note that HOMO, LUMO, E_T1The absolute value of (A) depends on the measurement or calculation method used, and even for the same method, different evaluations are madeFor example, the starting point and the peak point on the CV curve may give different HOMO/LUMO values. Thus, a reasonably meaningful comparison should be made with the same measurement method and the same evaluation method. In the description of the embodiments of the present invention, HOMO, LUMO, E_T1Is based on the simulation of the Time-dependent DFT but does not affect the application of other measurement or calculation methods.

In the present invention, (HOMO-1) is defined as the second highest occupied orbital level, (HOMO-2) is defined as the third highest occupied orbital level, and so on. (LUMO +1) is defined as the second lowest unoccupied orbital level, (LUMO +2) is the third lowest occupied orbital level, and so on.

In the invention, among the substituents

Represents the attachment site of the substituent, for example:

represents an optional substitution on the dibenzofuran ring.

The invention provides a naphthalocarbazole-containing organic compound shown as a structural formula (1-1) or (1-2):

wherein:

Ar₁、Ar₂each independently selected from a substituted or unsubstituted aryl or heteroaryl group having 5 to 30 ring atoms, or from a substituted or unsubstituted non-aromatic ring group having 5 to 30 ring atoms;

R₁、R₂each independently selected from H, D, straight chain alkyl having 1 to 20C atoms, alkoxy having 1 to 20C atoms, thioalkoxy having 3 to 20C atomsA branched or cyclic alkyl group having 3 to 20C atoms, a branched or cyclic alkoxy group having 3 to 20C atoms, a branched or cyclic thioalkoxy group having 3 to 20C atoms, a silyl group, a ketone group having 1 to 20C atoms, an alkoxycarbonyl group having 2 to 20C atoms, an aryloxycarbonyl group having 7 to 20C atoms, a cyano group, a carbamoyl group, a haloformyl group, a formyl group, an isocyano group, an isocyanate group, a thiocyanate group, an isothiocyanate group, a hydroxyl group, a nitro group, CF₃Cl, Br, F, a crosslinkable group, a substituted or unsubstituted aromatic or heteroaromatic group having 5 to 30 ring atoms, an aryloxy or heteroaryloxy group having 5 to 30 ring atoms, or a combination of these systems;

a is 1,2,3 or 4;

b is 1,2,3,4, 5 or 6;

wherein a represents R on a benzene ring₁The number of the substituents, b represents R on the naphthalene ring₂The number of substituents;

when there are more than one R₁When a plurality of R₁Are the same or different from each other; when there are more than one R₂When a plurality of R₂Are the same or different from each other;

each Z₁Independently selected from CR₃Or N, at least one Z₁Is N; r₃Is as defined for R₁。

In certain preferred embodiments, two Z' s₁Are all N.

In a preferred embodiment, R₁、R₂Each independently selected from H, D, a straight chain alkyl group having 1 to 20C atoms, an alkoxy group having 1 to 10C atoms, a thioalkoxy group having 1 to 10C atoms, a branched or cyclic alkyl group having 3 to 10C atoms, a branched or cyclic alkoxy group having 3 to 10C atoms, a branched or cyclic thioalkoxy group having 3 to 10C atoms, a silyl group, a ketone group having 1 to 10C atoms, an alkoxycarbonyl group having 2 to 10C atoms, an aryloxycarbonyl group having 7 to 10C atoms, a cyano group, a carbamoyl group, a haloformyl group, a formyl group, an isocyano group, an isocyanate group, a thiocyanate group, an isothiocyanate group, a hydroxyether group, a haloformyl group, an isocyanato group, a hydroxyl group, a substituted aryl groupRadical, nitro radical, CF₃Cl, Br, F, a crosslinkable group, a substituted or unsubstituted aromatic or heteroaromatic group having 5 to 30 ring atoms, an aryloxy or heteroaryloxy group having 5 to 30 ring atoms, or a combination of these systems.

An aromatic group refers to a hydrocarbon group containing at least one aromatic ring, including monocyclic groups and polycyclic ring systems. Heteroaromatic groups refer to hydrocarbon groups (containing heteroatoms) that contain at least one heteroaromatic ring, including monocyclic groups and polycyclic ring systems. These polycyclic rings may have two or more rings in which two carbon atoms are shared by two adjacent rings, i.e., fused rings. At least one of these ring species of the polycyclic ring is aromatic or heteroaromatic. The heteroatoms in the heteroaromatic are preferably selected from Si, N, P, O, S and/or Ge, particularly preferably from Si, N, P, O and/or S. For the purposes of the present invention, aromatic or heteroaromatic groups include not only aromatic or heteroaromatic systems, but also systems in which a plurality of aryl or heteroaryl groups may also be interrupted by short nonaromatic units (for example < 10% of non-H atoms, 5% of non-H atoms, such as C, N or O atoms). Thus, for example, systems such as 9,9' -spirobifluorene, 9, 9-diarylfluorene, triarylamines, diaryl ethers, etc., are also considered aromatic groups for the purposes of this invention.

Specifically, preferred examples of the aromatic group are: benzene, naphthalene, anthracene, phenanthrene, perylene, tetracene, pyrene, benzopyrene, triphenylene, acenaphthene, fluorene, and derivatives thereof.

Specifically, preferred examples of the heteroaromatic group are: furan, benzofuran, thiophene, benzothiophene, pyrrole, pyrazole, triazole, imidazole, oxazole, oxadiazole, thiazole, tetrazole, indole, carbazole, pyrroloimidazole, pyrrolopyrrole, thienopyrrole, thienothiophene, furopyrrole, furofuran, thienofuran, benzisoxazole, benzisothiazole, benzimidazole, pyridine, pyrazine, pyridazine, pyrimidine, triazine, quinoline, isoquinoline, phthalazine, quinoxaline, phenanthridine, primadine, quinazoline, quinazolinone, and derivatives thereof.

Further, for the purposes of the present invention, the substituent R₁、R₂Can be selected from (1)C1-C10 alkyl, particularly preferably the following groups: methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, 2-methylbutyl, n-pentyl, n-hexyl, cyclohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoromethyl, 2,2, 2-trifluoroethyl, ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl, and octynyl; (2) C1-C10 alkoxy, particularly preferably methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy or 2-methylbutoxy; (3) c2 to C10 aryl or heteroaryl, which may be monovalent or divalent depending on the use, in each case also by the abovementioned radicals R³Substituted and may be attached to the aromatic or heteroaromatic ring in any desired position, particularly preferred are the following groups: benzene, naphthalene, anthracene, pyrene, chrysene, perylene, fluoranthene, tetracene, pentacene, benzopyrene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzofluorene, pyrrole, indole, isoindole, carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5, 6-quinoline, benzo-6, 7-quinoline, benzo-7, 8-quinoline, phenothiazine, phenoxazine, pyrazole, indazole, imidazole, benzimidazole, naphthoimidazole, phenanthroimidazole, pyridoimidazole, pyrazinoimidazole, quinoxalimidazole, oxazole, benzoxazole, naphthoxazole, anthraoxazole, phenanthroizole, isoxazole, 1, 2-thiazole, 1, 3-thiazole, benzothiazole, pyridazine, benzopyrazine, pyrimidine, benzopyrimidine, quinoxaline, Pyrazine, diazaanthracene, 1, 5-naphthyridine, azocarbazole, benzocarbazine, phenanthroline, 1,2, 3-triazole, 1,2, 4-triazole, benzotriazole, 1,2, 3-oxadiazole, 1,2, 4-oxadiazole, 1,2, 5-oxadiazole, 1,3, 4-oxadiazole, 1,2, 3-thiadiazole, 1,2, 4-thiadiazole, 1,2, 5-thiadiazole, 1,3, 4-thiadiazole, 1,3, 5-triazine, 1,2, 4-triazine, 1,2, 3-triazine, tetrazole. 1,2,4, 5-tetrazine, 1,2,3, 4-tetrazine, 1,2,3, 5-tetrazinePurine, pteridine, indolizine and benzothiadiazole. For the purposes of the present invention, aromatic and heteroaromatic ring systems mean, in addition to the abovementioned aryl and heteroaryl groups, biphenylene, terphenylene, fluorene, spirobifluorene, dihydrophenanthrene, tetrahydropyrene and cis-or trans-indenofluorene.

In a preferred embodiment, the organic compound according to the invention, Ar₁、Ar₂Selected from aryl or heteroaryl of 5 to 30 ring atoms; in a more preferred embodiment, Ar is₁、Ar₂Selected from aryl or heteroaryl of 5 to 25 ring atoms; in a more preferred embodiment, Ar is₁、Ar₂Selected from aryl or heteroaryl of 6 to 20 ring atoms;

in a preferred embodiment, the organic compound according to the invention, Ar₁、Ar₂Is a group having at least one of the following structures:

wherein:

when there are more than one in the same group, each X is independently selected from N or CR₅；

When there are more than one in the same group, each Y is independently selected from CR₆R₇，SiR₆R₇，NR₆Or, C (═ O), S, or O;

R₅、R₆、R₇has the same meaning as R₁；

Further, the organic compound according to the present invention, said Ar₁、Ar₂Can be selected from one or more combinations of the following structural groups, and can be further randomly substituted:

in some further embodiments, according toA compound of formula (1-1) or formula (1-2), wherein Ar₁,Ar₂In multiple occurrences, the following structural units, or combinations thereof, may be included, identically or differently:

wherein n is 1,2,3 or 4.

In certain preferred embodiments, the naphthalene carbazole-containing organic compound has (S1-T1) an eV less than or equal to 0.3eV, preferably less than or equal to 0.25eV, more preferably less than or equal to 0.2eV, and most preferably less than or equal to 0.10 eV.

In other preferred embodiments, Ar in the above naphthalocarbazole-containing organic compound₂Comprises an electron-donating group. Suitable electron donating groups may be selected from the group consisting of:

in one embodiment, Ar₁、Ar₂Each independently selected from the group consisting of:

wherein A is O, S, N-Ph or CR₈R₉,，R₈、R₉Each independently is a C1-C6 alkyl group.

In one embodiment, R₈Is methyl, R₉Is methyl.

In one embodiment, Ar₁、Ar₂Each independently selected from the group consisting of:

the naphthaline carbazole-containing organic compound can be used as a functional material for electronic devices. Organic functional materials can be classified into Hole Injection Materials (HIM), Hole Transport Materials (HTM), Electron Transport Materials (ETM), Electron Injection Materials (EIM), Electron Blocking Materials (EBM), Hole Blocking Materials (HBM), emitters (Emitter), and Host materials (Host). In a preferred embodiment, the naphthalene carbazole-containing organic compound may be used as a host material, an electron transport material, or a hole transport material. In a more preferred embodiment, the naphthalene carbazole-containing organic compound is used as a phosphorescent host material.

As a phosphorescent host material, it must have an appropriate triplet energy level, E_T1. In certain embodiments, E of the above naphthazole-containing organic compound_T1More preferably not less than 2.3eV, still more preferably not less than 2.4eV, still more preferably not less than 2.5eV, still more preferably not less than 2.6eV, and most preferably not less than 2.7 eV.

Good thermal stability is desired as a phosphorescent host material. In one embodiment, the above-mentioned naphthalene carbazole-containing organic compound has a glass transition temperature Tg of 100 deg.C or higher, in a preferred embodiment 120 deg.C or higher, in a more preferred embodiment 140 deg.C or higher, in a more preferred embodiment 160 deg.C or higher, and in a most preferred embodiment 180 deg.C or higher.

In certain preferred embodiments, the naphthalene carbazole-containing organic compound ((HOMO- (HOMO-1)) >0.2eV, preferably 0.25eV, more preferably 0.3eV, even more preferably 0.35eV, even more preferably 0.4eV, and most preferably 0.45 eV.

In other preferred embodiments, the above naphthalocarbazole-containing organic compound has a (. di ((LUMO +1) -LUMO) > 0.15eV, preferably 0.20eV, more preferably 0.25eV, still more preferably 0.30eV, and most preferably 0.35 eV.

In some embodiments, the organic compound containing naphthalene carbazole has a light-emitting function, and the light-emitting wavelength is between 300 and 1000nm, preferably between 350 and 900nm, and more preferably between 400 and 800 nm. Luminescence as used herein refers to photoluminescence or electroluminescence.

In a preferred embodiment, the naphthalene carbazole-containing organic compound is preferably selected from, but not limited to, the following structures, which may be optionally substituted.

The invention further relates to a high polymer containing the naphthaline carbazole, and the repeating unit of the high polymer containing the naphthaline carbazole comprises the structure of the organic compound containing the naphthaline carbazole.

In a preferred embodiment, the above-mentioned naphthalene carbazole-containing polymer is synthesized by a method selected from the group consisting of SUZUKI-, YAMAMOTO-, STILLE-, NIGESHI-, KUMADA-, HECK-, SONOGASHIRA-, HIYAMA-, FUKUYAMA-, HARTWIG-BUCHWALD-and ULLMAN.

In a preferred embodiment, the glass transition temperature (Tg) of the naphthocarbazole-containing polymer is not less than 100 deg.C, preferably not less than 120 deg.C, more preferably not less than 140 deg.C, still more preferably not less than 160 deg.C, and most preferably not less than 180 deg.C.

In a preferred embodiment, the molecular weight distribution (PDI) of the naphthalene carbazole-containing polymer preferably ranges from 1 to 5; more preferably 1 to 4; more preferably 1 to 3, more preferably 1 to 2, and most preferably 1 to 1.5.

In a preferred embodiment, the weight average molecular weight (Mw) of the naphthalene carbazole-containing polymer is preferably in the range of 1 to 100 ten thousand; more preferably 5 to 50 ten thousand; more preferably 10 to 40 ten thousand, still more preferably 15 to 30 ten thousand, and most preferably 20 to 25 ten thousand.

The invention also relates to a naphthalocarbazole-containing mixture, which comprises the organic compound and at least one organic functional material. The organic functional material comprises a hole (also called hole) injection or transmission material (HIM/HTM), a Hole Blocking Material (HBM), an electron injection or transmission material (EIM/ETM), an Electron Blocking Material (EBM), an organic Host material (Host), a singlet state light emitter (fluorescent light emitter), a triplet state light emitter (phosphorescent light emitter), especially a light emitting organic metal complex, and an organic thermal excitation delayed fluorescence material (TADF material). Various organic functional materials are described in detail, for example, in WO2010135519a1, US20090134784a1 and WO2011110277a1, the entire contents of this 3 patent document being hereby incorporated by reference. The organic functional material can be small molecule and high polymer material.

In certain embodiments, the naphthazole-containing mixture comprises at least one naphthazole-containing organic compound or naphthazole-containing high polymer described above and a fluorescent light emitter. The naphthaline carbazole-containing organic compound or naphthaline carbazole-containing high polymer is used as a fluorescent main material, wherein the fluorescent luminous body is less than or equal to 10 wt%, preferably less than or equal to 9 wt%, more preferably less than or equal to 8 wt%, particularly preferably less than or equal to 7 wt%, and most preferably less than or equal to 5 wt%.

In a particularly preferred embodiment, the naphthazole-containing mixture comprises at least one naphthazole-containing organic compound or naphthazole-containing high polymer as described above and a phosphorescent emitter. The naphthaline carbazole-containing organic compound or naphthaline carbazole-containing high polymer is used as a phosphorescent main material, wherein the weight percentage of the phosphorescent luminous body is less than or equal to 25 wt%, preferably less than or equal to 20 wt%, and more preferably less than or equal to 15 wt%.

In another preferred embodiment, the naphthazole-containing mixture comprises at least one naphthazole-containing organic compound or naphthazole-containing high polymer, a phosphorescent emitter and a second host material. In this embodiment, the weight ratio of the organic compound containing naphthazole or high polymer containing naphthazole to the phosphorescent emitter is from 1:2 to 2: 1. In another preferred embodiment, the naphthalene carbazole-containing organic compound or the naphthalene carbazole-containing high polymer and the second host material form an exciplex, and the energy level of the exciplex is higher than that of the phosphorescent emitter.

In another preferred embodiment, the naphthalene carbazole-containing mixture comprises at least one of the above naphthalene carbazole-containing organic compounds or naphthalene carbazole-containing high polymers, and a TADF material. The naphthalene carbazole-containing organic compound or naphthalene carbazole-containing high polymer is used as a main material of the TADF luminescent material, wherein the weight percentage of the TADF material is less than or equal to 15 wt%, preferably less than or equal to 10 wt%, and more preferably less than or equal to 8 wt%.

In a very preferred embodiment, the naphthalene carbazole-containing mixture comprises at least one of the above naphthalene carbazole-containing organic compounds or naphthalene carbazole-containing high polymers, and a second host material. The organic compound according to the invention can be used as the first host in a proportion of 30 to 70% by weight, preferably 40 to 60% by weight.

In certain particularly preferred embodiments, the second host material has a structure represented by structural formula (2):

wherein Ar is₃,Ar₄Each independently selected from a substituted or unsubstituted aryl or heteroaryl group having 5 to 30 ring atoms, or a substituted or unsubstituted non-aromatic ring group having 5 to 30 ring atoms.

Preferably, the second host material may be selected from compounds having the following structures, which may be further optionally substituted.

Some more details (but not limited to) of fluorescent light emitting materials or singlet emitters, phosphorescent light emitting materials or triplet emitters, and TADF materials are described below.

1. Singlet state luminophor (Singlet Emitter)

Singlet emitters tend to have longer conjugated pi-electron systems. Hitherto, there have been many examples such as styrylamine and its derivatives disclosed in JP2913116B and WO2001021729a1, indenofluorene and its derivatives disclosed in WO2008/006449 and WO2007/140847, and triarylamine derivatives of pyrene disclosed in US7233019, KR 2006-0006760.

In a preferred embodiment, the singlet emitters may be selected from the group consisting of monostyrenes, distyrenes, tristyrenes, tetrastyrenes, styrylphosphines, styryl ethers, and arylamines.

A monostyrene amine is a compound comprising an unsubstituted or substituted styryl group and at least one amine, preferably an aromatic amine. A distyrene amine refers to a compound comprising two unsubstituted or substituted styryl groups and at least one amine, preferably an aromatic amine. A tristyrenylamine refers to a compound comprising three unsubstituted or substituted styrene groups and at least one amine, preferably an aromatic amine. A tetrastyrene amine refers to a compound comprising four unsubstituted or substituted styrene groups and at least one amine, preferably an aromatic amine. One preferred styrene is stilbene, which may be further substituted. The corresponding phosphines and ethers are defined analogously to the amines. Arylamine or aromatic amine refers to a compound comprising three unsubstituted or substituted aromatic rings or heterocyclic systems directly linked to nitrogen. At least one of these aromatic or heterocyclic ring systems is preferably a fused ring system and preferably has at least 14 aromatic ring atoms. Among them, preferred examples are aromatic anthracenamines, aromatic anthracenediamines, aromatic pyrenediamines, aromatic chrysenamines and aromatic chrysenediamines. An aromatic anthracylamine refers to a compound in which a diarylamine group is attached directly to the anthracene, preferably at the 9 position. An aromatic anthracenediamine refers to a compound in which two diarylamine groups are attached directly to the anthracene, preferably at the 9,10 positions. Aromatic pyrene amines, aromatic pyrene diamines, aromatic chrysene amines and aromatic chrysene diamines are similarly defined, wherein the diarylamine groups are preferably attached to the 1 or 1,6 position of pyrene.

Examples, also preferred, of singlet emitters based on vinylamines and arylamines can be found in WO 2006/000388, WO 2006/058737, WO 2006/000389, WO 2007/065549, WO 2007/115610, US 7250532B 2, DE 102005058557A 1, CN 1583691A, JP 08053397A, US 6251531B 1, US 2006/210830A, EP 1957606A 1 and US 2008/0113101A 1 and the entire contents of the patent documents listed above are hereby incorporated by reference.

An example of singlet emitters based on stilbene and its derivatives is US 5121029.

Further preferred singlet emitters may be selected from indenofluorene-amines and indenofluorene-diamines, as disclosed in WO 2006/122630, benzindenofluorene-amines and benzindenofluorene-diamines, as disclosed in WO2008/006449, dibenzoindenofluorene-amines and dibenzoindenofluorene-diamines, as disclosed in WO 2007/140847.

Further preferred singlet emitters may be selected from fluorene based fused ring systems as disclosed in US2015333277a1, US2016099411a1, US2016204355a 1.

More preferred singlet emitters may be selected from pyrene derivatives, such as the structures disclosed in US2013175509a 1; triarylamine derivatives of pyrene, such as pyrene triarylamine derivatives containing dibenzofuran units as disclosed in CN 102232068B; other triarylamine derivatives of pyrene having specific structures are disclosed in CN105085334A, CN 105037173A. Other materials which can be used as singlet emitters are polycyclic aromatic compounds, in particular derivatives of anthracene, such as 9, 10-bis (2-naphthoanthracene), naphthalene, tetraphene, xanthene, phenanthrene, pyrene, such as 2,5,8, 11-tetra-t-butylperylene, indenopyrene, phenylene, such as (4,4 '-bis (9-ethyl-3-carbazolyl-vinyl) -1, 1' -biphenyl, diindenopyrene, decacycloalkene, coronene, fluorene, spirobifluorene, arylpyrene, such as U.S. 20060222886, aryleneethene, such as U.S. Pat. No. 5121029, U.S. Pat. No. 5,8803, cyclopentadiene, such as tetraphenylcyclopentadiene, rubrene, coumarin, rhodamine, quinacridone, pyrans, such as 4 (dicyanomethylene) -6- (4-p-dimethylaminostyryl-2-methyl) -4H-pyran (DCM), thiopyran, bis (azinyl) iminoboron compounds (US 2007/0092753 a1), bis (azinyl) methylene compounds, carbostyryl compounds, oxazinones, benzoxazoles, benzothiazoles, benzimidazoles and pyrrolopyrrolediones. Some singlet emitter materials can be found in the patent documents US 20070252517A 1, US 4769292, US 6020078, US 2007/0252517A 1, US 2007/0252517A 1. The entire contents of the above listed patent documents are hereby incorporated by reference.

Some examples of suitable singlet emitters are listed in the following table:

2. triplet Emitter (Triplet Emitter)

Triplet emitters are also known as phosphorescent emitters. In a preferred embodiment, the triplet emitter is a metal complex of the formula M (L) n, wherein M is a metal atom, L, which may be the same or different at each occurrence, is an organic ligand which is bonded or coordinately bound to the metal atom M via one or more positions, and n is an integer greater than 1, preferably 1,2,3,4, 5 or 6. Optionally, the metal complexes are coupled to a polymer through one or more sites, preferably through organic ligands.

In a preferred embodiment, the metal atom M is chosen from transition metals or lanthanides or actinides, preferably Ir, Pt, Pd, Au, Rh, Ru, Os, Sm, Eu, Gd, Tb, Dy, Re, Cu or Ag, particularly preferably Os, Ir, Ru, Rh, Re, Pd, Au or Pt.

Preferably, the triplet emitter comprises a chelating ligand, i.e. a ligand, which coordinates to the metal via at least two binding sites, particularly preferably the triplet emitter comprises two or three identical or different bidentate or polydentate ligands. Chelating ligands are advantageous for increasing the stability of the metal complex.

Examples of organic ligands may be selected from phenylpyridine derivatives, 7, 8-benzoquinoline derivatives, 2 (2-thienyl) pyridine derivatives, 2 (1-naphthyl) pyridine derivatives, or 2-phenylquinoline derivatives. All of these organic ligands may be substituted, for example, with fluorine-containing or trifluoromethyl groups. The ancillary ligand may preferably be selected from acetone acetate or picric acid.

In a preferred embodiment, the metal complexes which can be used as triplet emitters are of the form:

where M is a metal selected from the transition metals or the lanthanides or actinides, particularly preferably Ir, Pt, Au;

Ar₁each occurrence of which may be the same or different, is a cyclic group containing at least one donor atom, i.e., an atom having a lone pair of electrons, such as nitrogen or phosphorus, through which the cyclic group is coordinately bound to the metal; ar (Ar)₂Each occurrence, which may be the same or different, is a cyclic group containing at least one C atom through which the cyclic group is attached to the metal; ar (Ar)₁And Ar₂Linked together by a covalent bond, which may each carry one or more substituent groups, which may in turn be linked together by substituent groups; l', which may be the same or different at each occurrence, is a bidentate chelating ancillary ligand, preferably a monoanionic bidentate chelating ligand; x may be 0,1,2 or 3, preferably 2 or 3; y may be 0,1,2 or 3, preferably 1 or 0.

Examples of materials and their use for some triplet emitters can be found in WO 200070655, WO 200141512, WO 200202714, WO 200215645, EP 1191613, EP 1191612, EP 1191614, WO 2005033244, WO 2005019373, US 2005/0258742, WO 2009146770, WO 2010015307, WO 2010031485, WO 2010054731, WO 2010054728, WO 2010086089, WO 2010099852, WO 2010099852, US 2010099852A 2010099852, US 2010099852A 2010099852, Baldo, Thompson et al. Nature 403, (2000), 750-and 753, US 2010099852A 2010099852, US 2010099852A 2010099852, Adachi. Appl. Phyt. Lett.78(2001), 1622-and 1624, J.Kido et al. Appl. Phys. Lett.65(1994), U.Kido.Phyt. 364, Chedo.657, US 2010099852, US 2010099852A 2010099852, US 2010099852A 2010099852, US 2010099852A 2010099852, US 2010099852A 3655, US 2010099852, US 2010099852, US 2010099852, US 2010099852A 2010099852, US 2010099852A 2010099852, US 2010099852A 3655, US 364, US 2010099852A 364, US 3655, US 2010099852A 3655, US 2010099852, US 2010099852A 3655, US 364, US 3655A 364, US 36753, US 2010099852, US 2010099852, US 2010099852, US 2010099852A 2010099852, US 2010099852, US 2010099852, US 2010099852A 2010099852, US 2010099852, US 364, US 2010099852, US 2010099852, US 2010099852, US 2010099852, US 364, US 2010099852A 2010099852, US 2010099852, US 364, US 369A 2010099852, US 2010099852, US 2010099852, US 369A 364, US 369A 369, US 364, US 369A 36753, US 364, US 369A 369, US 369A 369, US 364, US 369, WO 2012007088a1, WO2012007087a1, WO 2012007086a1, US 2008027220a1, WO 2011157339a1, CN 102282150a, WO 2009118087a1, WO 2013107487a1, WO 2013094620a1, WO 2013174471a1, WO 2014031977a1, WO 2014112450a1, WO 2014007565a1, WO 2014038456a1, WO 2014024131a1, WO 2014008982A1, WO2014023377a 1. The entire contents of the above listed patent documents and literature are hereby incorporated by reference.

Some examples of suitable triplet emitters are listed in the following table:

3. thermally activated delayed fluorescence luminescent material (TADF):

the traditional organic fluorescent material can only emit light by utilizing 25% singlet excitons formed by electric excitation, and the internal quantum efficiency of the device is low (up to 25%). Although the phosphorescence material enhances the intersystem crossing due to the strong spin-orbit coupling of the heavy atom center, the singlet excitons and the triplet excitons formed by the electric excitation can be effectively used for emitting light, so that the internal quantum efficiency of the device reaches 100 percent. However, the application of the phosphorescent material in the OLED is limited by the problems of high price, poor material stability, serious efficiency roll-off of the device and the like. The thermally activated delayed fluorescence emitting material is a third generation organic emitting material developed after organic fluorescent materials and organic phosphorescent materials. Such materials typically have a small singlet-triplet energy level difference (Δ E)_st) The triplet excitons may be converted to singlet excitons by intersystem crossing to emit light. This makes full use of singlet excitons formed under electrical excitationAnd triplet excitons. The quantum efficiency in the device can reach 100%. Meanwhile, the material has controllable structure, stable property, low price and no need of noble metal, and has wide application prospect in the field of OLED.

TADF materials need to have a small singlet-triplet level difference, preferably Δ Est <0.3eV, less preferably Δ Est <0.25eV, more preferably Δ Est <0.20eV, and most preferably Δ Est <0.1 eV. In a preferred embodiment, the TADF material has a relatively small Δ Est, and in another preferred embodiment, the TADF has a good fluorescence quantum efficiency. Some TADF luminescent materials may be found in patent documents CN103483332(a), TW201309696(a), TW201309778(a), TW201343874(a), TW201350558(a), US20120217869(a1), WO2013133359(a1), WO2013154064(a1), Adachi, et. al. adv.mater, 21,2009,4802, Adachi, et. al. appl.phys.lett.,98,2011,083302, Adachi, et. appl.phys.lett, 101,2012,093306, Adachi, chem.comm.comm, 48,2012,11392, Adachi, et. nature. natronics, 6,2012,253, Adachi, et. nature,492,2012,234, Adachi, am.j.am, Adachi, et. adochi, et. nature, adochi, et. phytol.73, adochi, et. phyton.8, Adachi, adachi.73, et. phytol.73, Adachi, et. phyton.73, et. phytol.35, Adachi, et. phytol.8, Adachi, adachi.t.t.t.

It is an object of the present invention to provide a material solution for evaporation type OLEDs.

In certain embodiments, the above-described naphthalocarbazole-containing organic compounds have a molecular weight of 1100g/mol or less, preferably 1000g/mol or less, more preferably 950g/mol or less, more preferably 900g/mol or less, and most preferably 800g/mol or less.

It is another object of the present invention to provide a material solution for printing OLEDs.

In some embodiments, the molecular weight of the above mentioned naphthaline-carbazole-containing organic compounds is 700g/mol or more, preferably 900g/mol or more, very preferably 900g/mol or more, more preferably 1000g/mol or more, and most preferably 1100g/mol or more.

In other embodiments, the above naphthaline-containing carbazole-based compounds have a solubility in toluene of 10mg/ml or more, preferably 15mg/ml or more, and most preferably 20mg/ml or more at 25 ℃.

The invention also relates to a naphthaline carbazole-containing composition or ink, which comprises at least one naphthaline carbazole-containing organic compound or naphthaline carbazole-containing high polymer and at least one organic solvent.

For the printing process, the viscosity of the ink, surface tension, is an important parameter. Suitable inks have surface tension parameters suitable for a particular substrate and a particular printing process.

In a preferred embodiment, the surface tension of the ink according to the invention at operating temperature or at 25 ℃ is in the range of about 19dyne/cm to about 50 dyne/cm; more preferably in the range of 22dyne/cm to 35 dyne/cm; preferably in the range of 25dyne/cm to 33 dyne/cm.

In another preferred embodiment, the viscosity of the ink according to the invention is in the range of about 1cps to about 100cps at the operating temperature or 25 ℃; preferably in the range of 1cps to 50 cps; more preferably in the range of 1.5cps to 20 cps; preferably in the range of 4.0cps to 20 cps. The composition so formulated will facilitate ink jet printing.

The viscosity can be adjusted by different methods, such as by appropriate solvent selection and concentration of the functional material in the ink. The inks according to the invention comprising the organometallic complexes or polymers described facilitate the adjustment of the printing inks to the appropriate range according to the printing process used. Generally, the composition according to the present invention comprises the functional material in a weight ratio ranging from 0.3% to 30% by weight, preferably ranging from 0.5% to 20% by weight, more preferably ranging from 0.5% to 15% by weight, still more preferably ranging from 0.5% to 10% by weight, and most preferably ranging from 1% to 5% by weight.

In some embodiments, the ink according to the invention, the at least one organic solvent is chosen from aromatic or heteroaromatic-based solvents, in particular aliphatic chain/ring-substituted aromatic solvents, or aromatic ketone solvents, or aromatic ether solvents.

Examples of solvents suitable for the present invention are, but not limited to: aromatic or heteroaromatic-based solvents p-diisopropylbenzene, pentylbenzene, tetrahydronaphthalene, cyclohexylbenzene, chloronaphthalene, 1, 4-dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, dipentylbenzene, tripentylbenzene, pentyltoluene, o-xylene, m-xylene, p-xylene, o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, 1,2,3, 4-tetramethylbenzene, 1,2,3, 5-tetramethylbenzene, 1,2,4, 5-tetramethylbenzene, butylbenzene, dodecylbenzene, dihexylbenzene, dibutylbenzene, p-diisopropylbenzene, 1-methoxynaphthalene, cyclohexylbenzene, dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, 1-methylnaphthalene, 1,2, 4-trichlorobenzene, 1, 3-dipropoxybenzene, 4-difluorodiphenylmethane, 1, 2-dimethoxy-4- (1-propenyl) benzene, 1, 4-dimethoxynaphthalene, Diphenylmethane, 2-phenylpyridine, 3-phenylpyridine, N-methyldiphenylamine, 4-isopropylbiphenyl, dichlorodiphenylmethane, 4- (3-phenylpropyl) pyridine, benzyl benzoate, 1-bis (3, 4-dimethylphenyl) ethane, 2-isopropylnaphthalene, dibenzyl ether, etc.; ketone-based solvents 1-tetralone, 2- (phenylepoxy) tetralone, 6- (methoxy) tetralone, acetophenone, propiophenone, benzophenone, and derivatives thereof, such as 4-methylacetophenone, 3-methylacetophenone, 2-methylacetophenone, 4-methylpropiophenone, 3-methylpropiophenone, 2-methylpropiophenone, isophorone, 2,6, 8-trimethyl-4-nonanone, fenchyne, 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone, 2, 5-hexanedione, phorone, di-n-amyl ketone; aromatic ether solvent: 3-phenoxytoluene, butoxybenzene, benzylbutylbenzene, p-anisaldehyde dimethylacetal, tetrahydro-2-phenoxy-2H-pyran, 1, 2-dimethoxy-4- (1-propenyl) benzene, 1, 4-benzodioxane, 1, 3-dipropylbenzene, 2, 5-dimethoxytoluene, 4-ethylbenylether, 1,2, 4-trimethoxybenzene, 4- (1-propenyl) -1, 2-dimethoxybenzene, 1, 3-dimethoxybenzene, glycidylphenyl ether, dibenzyl ether, 4-t-butylanisole, trans-p-propenylanisole, 1, 2-dimethoxybenzene, 1-methoxynaphthalene, diphenyl ether, 2-phenoxymethyl ether, 2-phenoxytetrahydrofuran, and the like, Ethyl-2-naphthyl ether, amyl ether c-hexyl ether, dioctyl ether, ethylene glycol dibutyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol ethyl methyl ether, triethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether; ester solvent: alkyl octanoates, alkyl sebacates, alkyl stearates, alkyl benzoates, alkyl phenylacetates, alkyl cinnamates, alkyl oxalates, alkyl maleates, alkyl lactones, alkyl oleates, and the like.

Further, according to the ink of the present invention, the at least one organic solvent may be selected from: aliphatic ketones such as 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone, 2, 5-hexanedione, 2,6, 8-trimethyl-4-nonanone, phorone, di-n-amyl ketone and the like; or aliphatic ethers such as amyl ether, hexyl ether, dioctyl ether, ethylene glycol dibutyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol ethyl methyl ether, triethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, and the like.

In other embodiments, the printing ink further comprises another organic solvent. Examples of another organic solvent include (but are not limited to): methanol, ethanol, 2-methoxyethanol, methylene chloride, chloroform, chlorobenzene, o-dichlorobenzene, tetrahydrofuran, anisole, morpholine, toluene, o-xylene, m-xylene, p-xylene, 1, 4-dioxane, acetone, methyl ethyl ketone, 1, 2-dichloroethane, 3-phenoxytoluene, 1,1, 1-trichloroethane, 1,1,2, 2-tetrachloroethane, ethyl acetate, butyl acetate, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, tetrahydronaphthalene, decalin, indene, and/or mixtures thereof.

In a preferred embodiment, the above-mentioned naphthaline-containing carbazole-based composition is a solution.

In another preferred embodiment, the above-described naphthalene carbazole-containing composition is a suspension.

The above-mentioned naphthaline-carbazole-containing composition may contain 0.01 to 20% by weight of the naphthaline-carbazole-containing organic compound or naphthaline-carbazole-containing mixture according to the present invention, preferably 0.1 to 15% by weight, more preferably 0.2 to 10% by weight, most preferably 0.25 to 5% by weight of the naphthaline-carbazole-containing organic compound or naphthaline-carbazole-containing mixture.

The invention also relates to the use of the naphthazole-containing composition as a coating or printing ink in the preparation of organic electronic devices, particularly preferably a preparation method by printing or coating.

Suitable Printing or coating techniques include, but are not limited to, ink jet Printing, letterpress, screen Printing, dip coating, spin coating, doctor blade coating, roll Printing, twist roll Printing, lithographic Printing, flexographic Printing, rotary Printing, spray coating, brush or pad Printing, slot die coating, and the like. Ink jet printing, jet printing and gravure printing are preferred. The solution or suspension may additionally include one or more components such as surface active compounds, lubricants, wetting agents, dispersants, hydrophobing agents, binders, and the like, for adjusting viscosity, film forming properties, enhancing adhesion, and the like. For details on the printing technology and its requirements concerning the solutions, such as solvents and concentrations, viscosities, etc., reference is made to the Handbook of Print Media, technology and Production Methods, published by Helmut Kipphan, ISBN 3-540-67326-1.

Based on the Organic naphthalene carbazole-containing compound, the present invention also provides an application of the Organic naphthalene carbazole-containing compound as described above, i.e., applying the Organic naphthalene carbazole-containing compound or the high naphthalene carbazole-containing polymer to an Organic electronic device, wherein the Organic electronic device can be selected from, but not limited to, an Organic Light Emitting Diode (OLED), an Organic photovoltaic cell (OPV), an Organic light Emitting cell (OLEEC), an Organic Field Effect Transistor (OFET), an Organic light Emitting field effect transistor (fet), an Organic laser, an Organic spin electronic device, an Organic sensor, an Organic Plasmon Emitting Diode (Organic plasma Emitting Diode), and the like, and particularly preferably an Organic electroluminescent device, such as an OLED, an OLEEC, or an Organic light Emitting field effect transistor. In the embodiment of the present invention, the organic compound is preferably used for a light emitting layer of an electroluminescent device.

The invention further relates to an organic electronic device comprising at least one organic compound or polymer as described above. Generally, such an organic electronic device comprises at least a cathode, an anode and a functional layer disposed between the cathode and the anode, wherein the functional layer comprises at least one organic compound or polymer as described above. The Organic electronic device can be selected from, but not limited to, Organic Light Emitting Diodes (OLEDs), Organic photovoltaic cells (OPVs), Organic light Emitting cells (OLEECs), Organic Field Effect Transistors (OFETs), Organic light Emitting field effect transistors (fets), Organic lasers, Organic spintronic devices, Organic sensors, Organic Plasmon Emitting diodes (Organic Plasmon Emitting diodes), and the like, and particularly preferred are Organic electroluminescent devices such as OLEDs, OLEECs, Organic light Emitting field effect transistors.

In certain particularly preferred embodiments, the electroluminescent device comprises a light-emitting layer comprising one of the organic compounds, or comprising one of the organic compounds and a phosphorescent emitter, or comprising one of the organic compounds and a host material, or comprising one of the organic compounds, a phosphorescent emitter and a host material.

In the above-described electroluminescent device, in particular an OLED, comprising a substrate, an anode, at least one light-emitting layer, a cathode.

The substrate may be opaque or transparent. A transparent substrate may be used to fabricate a transparent light emitting device. See, for example, Bulovic et al Nature 1996,380, p29, and Gu et al, appl.Phys.Lett.1996,68, p 2606. The substrate may be rigid or flexible. The substrate may be plastic, metal, semiconductor wafer or glass. Preferably, the substrate has a smooth surface. A substrate free of surface defects is a particularly desirable choice. In a preferred embodiment, the substrate is flexible, and may be selected from polymeric films or plastics having a glass transition temperature Tg of 150 deg.C or greater, preferably greater than 200 deg.C, more preferably greater than 250 deg.C, and most preferably greater than 300 deg.C. Examples of suitable flexible substrates are poly (ethylene terephthalate) (PET) and polyethylene glycol (2, 6-naphthalene) (PEN).

The anode may comprise a conductive metal or metal oxide, or a conductive polymer. The anode can easily inject holes into a Hole Injection Layer (HIL) or a Hole Transport Layer (HTL) or an emission layer. In one embodiment, the absolute value of the difference between the work function of the anode and the HOMO level or valence band level of the emitter in the light emitting layer or the p-type semiconductor material acting as a HIL or HTL or Electron Blocking Layer (EBL) is less than 0.5eV, preferably less than 0.3eV, most preferably less than 0.2 eV. Examples of anode materials include, but are not limited to: al, Cu, Au, Ag, Mg, Fe, Co, Ni, Mn, Pd, Pt, ITO, aluminum-doped zinc oxide (AZO), and the like. Other suitable anode materials are known and can be readily selected for use by one of ordinary skill in the art. The anode material may be deposited using any suitable technique, such as a suitable physical vapor deposition method including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like. In certain embodiments, the anode is pattern structured. Patterned ITO conductive substrates are commercially available and can be used to prepare devices according to the present invention.

The cathode may comprise a conductive metal or metal oxide. The cathode can easily inject electrons into the EIL or ETL or directly into the light emitting layer. In one embodiment, the absolute value of the difference between the work function of the cathode and the LUMO level or conduction band level of the emitter in the light-emitting layer or of the n-type semiconductor material as Electron Injection Layer (EIL) or Electron Transport Layer (ETL) or Hole Blocking Layer (HBL) is less than 0.5eV, preferably less than 0.3eV, most preferably less than 0.2 eV. In principle, all materials which can be used as cathodes in OLEDs are possible as cathode materials for the device according to the invention. Examples of cathode materials include, but are not limited to: al, Au, Ag, Ca, Ba, Mg, LiF/Al, MgAg alloy, BaF2/Al, Cu, Fe, Co, Ni, Mn, Pd, Pt, ITO, etc. The cathode material may be deposited using any suitable technique, such as a suitable physical vapor deposition method, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like.

The OLED may also comprise further functional layers, such as a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an Electron Blocking Layer (EBL), an Electron Injection Layer (EIL), an Electron Transport Layer (ETL), a Hole Blocking Layer (HBL). Suitable materials for use in these functional layers are described in detail above and in WO2010135519a1, US20090134784a1 and WO2011110277a1, the entire contents of these 3 patent documents being hereby incorporated by reference.

In a preferred embodiment, the light-emitting device according to the invention has a light-emitting layer which is prepared from a composition according to the invention.

The light-emitting device according to the present invention emits light at a wavelength of 300 to 1000nm, preferably 350 to 900nm, more preferably 400 to 800 nm.

The invention also relates to the use of the organic electronic device according to the invention in various electronic devices, including, but not limited to, display devices, lighting devices, light sources, sensors, etc.

The invention also relates to electronic devices including, but not limited to, display devices, lighting devices, light sources, sensors, etc., comprising the organic electronic device according to the invention.

The present invention will be described in connection with preferred embodiments, but the present invention is not limited to the following embodiments, and it should be understood that the appended claims outline the scope of the present invention and those skilled in the art, guided by the inventive concept, will appreciate that certain changes may be made to the embodiments of the invention, which are intended to be covered by the spirit and scope of the appended claims.

DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION

Example 1: synthesis of Compound 1

Synthesis of intermediate M2: 50g of 2-naphthylboronic acid, 94g of 2-nitro-4-bromo-1-iodobenzene and 10g of Pd (PPh)₃)₄Dissolved in 300mL of THF and 50mL of H₂And reacting the mixture in a mixed solvent of O for 24 hours at 80 ℃ in a nitrogen atmosphere. Spin-drying solvent, extracting with dichloromethane, washing with water, separating liquid, and performing column chromatography to obtain intermediate M2.MS (ASAP):328.17

Synthesis of intermediate M3: 40g of intermediate M2 were dissolved in 400mL of triethyl phosphite and reacted at 150 ℃ for 24 h. The solvent was distilled off under reduced pressure, and column chromatography was carried out to give intermediate M3.MS (ASAP):296.17.

Synthesis of intermediate M4: 35g of intermediate M3, 33g of pinacol diboron and Pd (dppf) Cl₂Dissolved in 300mL1, 4-dioxane, and stirred at 100 ℃ for 24h under nitrogen atmosphere. And (4) spin-drying the solvent, extracting, separating liquid, and performing column chromatography to obtain an intermediate M4.ASAP (343.23).

Synthesis of intermediate M5: 30g of intermediate M4, 23g of 2-chloro-4-phenylquinazoline, and 4.5g of intermediate M were dissolved in a mixed solvent of 300mL of toluene and 50mL of water, and the mixture was stirred at 100 ℃ for 24 hours under a nitrogen atmosphere. The solvent was distilled off under reduced pressure, and column chromatography was carried out to give intermediate M5.MS (ASAP):421.50.

Synthesis of materials 1-1: 25g of intermediate M5, 13.5g of iodobenzene, 16g of cuprous iodide, 13.5g of trans-cyclohexanediamine and 25g of potassium phosphate were dissolved in 300mL of dry toluene and stirred at 120 ℃ for 12h under a nitrogen atmosphere. And (3) distilling under reduced pressure to remove the solvent, washing with water, extracting, and carrying out column chromatography to obtain the compound 1.MS (ASAP) 497.62.

Example 2: synthesis of Compound 2

Synthesis of compound 2 the synthesis of compound 1 was referenced except iodobenzene was replaced with intermediate M6.

Example 3: synthesis of Compound 7

Compound 7 was synthesized according to example 1, except that iodobenzene was exchanged for intermediate M7.

Example 4: synthesis of Compound 24

Synthesis of compound 24 reference is made to the synthesis of material 1, except that the 2-chloro-4-phenylquinazoline in compound 1 is exchanged for the intermediate m8.ms (ASAP): 586.72.

example 5: synthesis of Compound 37

Synthesis of intermediate M11: 50g of 1-naphthylboronic acid, 94g of 2-nitro-4-bromo-1-iodobenzene and 10g of Pd (PPh)₃)₄Dissolve in 300mL THF and 50mL H₂And reacting the mixture in a mixed solvent of O for 24 hours at 80 ℃ in a nitrogen atmosphere. Removing solvent by rotary evaporation, extracting with dichloromethane, washing with water, separating liquid, and performing column chromatography to obtain intermediate M11.MS (ASAP):328.17

Synthesis of intermediate M12: 40g of intermediate M11 were dissolved in 400mL of triethyl phosphite and reacted at 150 ℃ for 24 h. The solvent was distilled off under reduced pressure, and column chromatography was carried out to give intermediate M12.MS (ASAP):296.17.

Synthesis of intermediate M13: 35g of intermediate M12, 33g of pinacol diboron and Pd (dppf) Cl₂Dissolved in 300mL1, 4-dioxane, and stirred at 100 ℃ for 24h under nitrogen atmosphere. The solvent is dried by spinning, extracted and separated, and the intermediate M13.ASAP (343.23) is obtained by column chromatography.

Synthesis of intermediate M14: 30g of intermediate M13, 23g of 2-chloro-4-phenylquinazoline, and 4.5g of intermediate M were dissolved in a mixed solvent of 300mL of toluene and 50mL of water, and the mixture was stirred at 100 ℃ for 24 hours under a nitrogen atmosphere. The solvent was distilled off under reduced pressure, and column chromatography was carried out to give intermediate M14.MS (ASAP):421.50.

Synthesis of compound 37: 25g of intermediate M14, 13.5g of iodobenzene, 16g of cuprous iodide, 13.5g of trans-cyclohexanediamine and 25g of potassium phosphate were dissolved in 300mL of dry toluene and stirred at 120 ℃ for 12h under a nitrogen atmosphere. The solvent was removed by distillation under the reduced pressure, washed with water, extracted, and subjected to column chromatography to give compound 37. MS (ASAP) 497.62.

Example 6: synthesis of Compound 15

Synthesis of compound 15 the synthesis of compound 1 was referenced except iodobenzene was replaced with intermediate M15. MS (ASAP) 712.86

Example 7: synthesis of Compound 47

Synthesis of compound 47 the synthesis of compound 37 was referenced except iodobenzene was replaced with intermediate M16. MS (ASAP) 712.86

Example 8: synthesis of Compound 65

Synthesis of intermediate M18 reference the synthesis of intermediate M14, except that 2-chloro-4-phenylquinazoline was replaced with M17 ms (asap) of intermediate M18: 588.71

Synthesis of compound 65 reference was made to the synthesis of compound 37 except intermediate M14 was replaced with intermediate M18. MS (ASAP) 664.81

Example 9: synthesis of Compound 66

Synthesis of compound 66 the synthesis of compound 37 was referenced except iodobenzene was replaced with intermediate M19. MS (ASAP) 647.78

Example 11: synthesis of Compound 39

Synthesis of compound 39 the synthesis of compound 37 was referenced except iodobenzene was replaced with intermediate M20. MS (ASAP) 547.66

Example 12: energy level of the compound

The energy level of the organic compound material can be obtained by quantum calculation, for example, by using TD-DFT (including time density functional theory) through Gaussian09W (Gaussian Inc.), and a specific simulation method can be seen in WO 2011141110. Firstly, a Semi-empirical method of 'group State/Semi-empirical/Default Spin/AM 1' (Charge 0/Spin Singlet) is used for optimizing the molecular geometrical structure, and then the energy structure of the organic molecules is calculated by a TD-DFT (including time density functional theory) method to obtain 'TD-SCF/DFT/Default Spin/B3PW 91' and a base group of '6-31G (d)' (Charge 0/Spin Singlet). The HOMO and LUMO energy levels are calculated according to the following calibration equation, S₁，T₁And c resonance factor f (S)₁) Can be used directly.

HOMO(eV)＝((HOMO(G)×27.212)-0.9899)/1.1206

LUMO(eV)＝((LUMO(G)×27.212)-2.0041)/1.385

Where HOMO (G) and LUMO (G) are direct calculations of Gaussian09W in Hartree. The results are shown in table 1:

table 1: energy level of the compound

Wherein, the LUMO values of all the compounds in accordance with the general formula (1) are close to-2.8 eV, and the triplet level T1 is above-2.40 eV, which shows that the compounds in accordance with the general formula (1) shown in the examples are all suitable red host materials. All compounds of the general formula (1) also have a large Δ HOMO and Δ LUMO (Δ LUMO >0.2 eV). Wherein, the compound 1, the compound 37 and the compound 47 can be respectively blended with F-1 and F-2 to be used as a main mixing body. The compounds corresponding to general formula (1) in table 1 can be blended with red phosphorescent emitters or TADF emitters R-1 as light-emitting layer materials.

Example 13: preparation and characterization of OLED devices

The device structure is ITO/NPD (60 nm)/compound 1 or 2 or 37 (piq)₂Ir (acac) (10%) (45nm)/TPBi (35nm)/Liq (1nm)/Al (150 nm). Wherein (piq)₂Ir (acac) as a light emitting material, NPD as a hole transporting material, TPBi as an electron transporting material, and Liq as an electron injecting material. The specific preparation process is as follows:

a. cleaning the conductive glass substrate, namely cleaning the conductive glass substrate by using various solvents such as chloroform, ketone and isopropanol when the conductive glass substrate is used for the first time, and then carrying out ultraviolet ozone plasma treatment;

b. HTL (60nm), EML (45nm), ETL (35 m): under high vacuum (1X 10)^-6Mbar, mbar) by thermal evaporation;

c. cathode-LiF/Al (1nm/150nm) in high vacuum (1X 10)^-6Millibar) hot evaporation;

d. encapsulation the devices were encapsulated with uv curable resin in a nitrogen glove box.

Table 2: OLED device Performance comparison

The current-voltage (J-V) characteristics of each OLED device were characterized by a characterization device, while recording important parameters such as efficiency, lifetime, and external quantum efficiency. Table 1 shows the OLED device lifetime comparison where lifetime LT95 is the time at which the luminance drops to 95% of the initial luminance @1000nits at constant current. Here LT95 is calculated relative to the device OLED9, i.e. with the lifetime of OLED4 being 1. Through detection, the service lives of the OLED1 (corresponding to the compound 1), the OLED2 (corresponding to the compound 2), the OLED3 (corresponding to the compound 37), the OLED4 (corresponding to the compound 15), the OLED5 (corresponding to the compound 47), the OLED6 (corresponding to the compound 65), the OLED7 (corresponding to the compound 66) and the OLED8 (corresponding to the compound 39) are all more than 3 times longer than those of the comparative device OLED9 (corresponding to the material CBP) and are obviously higher than those of the comparative device OLED10 (corresponding to the comparative compound F-1, refer to the document CN 103249800).

Example 14: characterization of OLED devices based on mixtures containing compounds of the general formulae (1) and (2)

Table 3: OLED device Performance comparison

OLED device	Host material	LT95@1000nits
			OLED11	1：F-2	7.3
OLED12	37：F-2	8.3
			OLED13	47：F-2	7.1
OLED14	37:F-3	7.5
			Contrast device OLED15	CBP：F-2	1
Contrast device OLED16	F-1：F-2	1.8

Devices OLED 11-16 were prepared with reference to example 13, except that the host material was replaced with a mixture as shown in table 3, wherein the mass ratio of the two components of the mixture was 1: 1. F-2 and F-3 are materials described in the structural formula (2) of the invention, and are specifically synthesized in reference CN 201680059397. The current-voltage (J-V) characteristics of each OLED device were characterized by a characterization device, while recording important parameters such as efficiency, lifetime, and external quantum efficiency. Table 3 shows the lifetime comparison of OLED devices, where lifetime LT95 is the time at which the luminance drops to 95% of the initial luminance @1000nits at constant current. LT95 is calculated here in relation to OLED15 (corresponding to mixture CBP: F-2), i.e. with the lifetime of OLED15 being 1. Through detection, the service lives of the OLED11 (corresponding to the mixture 1: F-2), the OLED12 (corresponding to the mixture 37: F-2), the OLED13 (corresponding to the mixture 47: F-2) and the OLED14 (corresponding to the mixture 37: F-3) are all more than 3 times that of the OLED15 (corresponding to the mixture CBP: F-2) and are obviously higher than that of the OLED16 (corresponding to the mixture F-1: F-2), and therefore, the service lives of the OLED devices prepared by the organic mixture are obviously prolonged.

Example 15: characterization of OLED devices based on mixtures of compounds of the general formula (1) with TADF emitters

Table 4: OLED device Performance comparison

OLED device	Host material	LT95@1000nits
			OLED17	1	2.9
OLED18	37	3.6
			OLED19	66	4.1
OLED20	39	4.3
			Contrast device OLED21	CBP	1
Contrast device OLED22	F-1	1.3

Preparation of devices OLED 17-OLED 22 referring to example 13, except that the host material was replaced with the compound shown in Table 4 and (piq)₂Ir (acac) was replaced with TADF emitter R-1(R-1 reference adv. Mater.2016, 181-187). The light-emitting layers of the devices OLED 17-OLED 22 were mixtures of host compounds and TADF emitters as shown in table 4. The current-voltage (J-V) characteristics of each OLED device are characterized by a characterization apparatusImportant parameters such as efficiency, lifetime and external quantum efficiency are recorded. Table 3 shows the lifetime comparison of OLED devices, where lifetime LT95 is the time at which the luminance drops to 95% of the initial luminance @1000nits at constant current. LT95 is calculated here in relation to OLED21 (corresponding to mixture CBP: R-1), i.e. with the lifetime of OLED21 being 1. Through detection, the service lives of the OLED17 (corresponding to the mixture 1: R-1), the OLED18 (corresponding to the mixture 37: R-1), the OLED18 (corresponding to the mixture 66: R-1) and the OLED19 (corresponding to the mixture 39: R-1) are more than 2 times of that of the OLED21 (corresponding to the mixture CBP: R-1) and are obviously higher than that of the OLED22 (corresponding to the mixture F-1: R-1), and therefore, the service lives of the OLED devices prepared by the organic mixture are obviously prolonged.

The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.

The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (8)

1. A naphthalocarbazole-containing organic compound characterized by having a structure represented by the structural formula (1-1) or the structural formula (1-2):

wherein: z₁Is N;

ar is₁、Ar₂Each independently selected from any one of the following groups:

a is O, S, N-Ph or CR₈R₉，R₈Is methyl, R₉Is methyl.

2. The naphthazole-containing organic compound of claim 1, wherein the Δ HOMO ≥ 0.3eV and/or Δ LUMO ≥ 0.2 eV; wherein Δ HOMO ═ HOMO- (HOMO-1) and Δ LUMO ═ (LUMO +1) -LUMO.

3. An organic compound containing a naphthaline carbazole, characterized in that it is selected from any one of the following compounds

4.A naphthazole-containing mixture comprising the naphthazole-containing organic compound of any one of claims 1 to 3 and a second host material having a structure represented by formula (2):

wherein Ar is₃,Ar₄Each independently selected from aryl or heteroaryl of 5 to 30 ring atoms.

5. A naphthazole-containing mixture comprising the naphthazole-containing organic compound of any one of claims 1 to 3 and any one of the following compounds:

6. a naphthazole-containing composition comprising at least one naphthazole-containing organic compound of any of claims 1-3, and at least one organic solvent.

7. An organic electronic device comprising at least one naphthalene carbazole-containing organic compound according to any one of claims 1 to 3 or a naphthalene carbazole-containing mixture according to claim 4 or 5.

8. An organic electronic device comprising a light-emitting layer containing the naphthazole-containing organic compound according to any one of claims 1 to 3 or the naphthazole-containing mixture according to claim 4 or 5.