CN109705100A

CN109705100A - The organic optical compounds of carbazoles containing naphthalene, mixture, composition and application thereof

Info

Publication number: CN109705100A
Application number: CN201811481021.4A
Authority: CN
Inventors: 潘君友; 张晨; 江广涛; 游雪强; 黄宏
Original assignee: Guangzhou Hua Rui Photoelectric Material Co Ltd
Current assignee: Guangzhou Hua Rui Photoelectric Material Co Ltd
Priority date: 2017-12-22
Filing date: 2018-12-05
Publication date: 2019-05-03
Anticipated expiration: 2038-12-05
Also published as: CN109705100B

Abstract

The present invention relates to a kind of organic compound of carbazoles containing naphthalene, mixture, composition and its applications, wherein the organic compound of carbazoles containing naphthalene has the structure as shown in structural formula (1-1) or structural formula (1-2):

Description

The organic optical compounds of carbazoles containing naphthalene, mixture, composition and application thereof

This application claims in submission on December 22nd, 2017 Patent Office of the People's Republic of China, application No. is 201711406898.2 invention names Referred to as the priority of the Chinese patent application of " one kind organic photoelectrical material of carbazoles containing naphthalene and application thereof ", entire contents pass through Reference is incorporated in the present application.

Technical field

The present invention relates to electroluminescent material fields, more particularly to the organic optical compounds of carbazoles containing naphthalene, mixture, combination Object and application thereof.

Background technique

Organic photoelectrical material has diversity, the optics and electricity that manufacturing cost is relatively low and its is excellent in synthesis Performance.Organic Light Emitting Diode (OLED) has wide view in the application aspect of photoelectric device (such as flat-panel monitor and illumination) Angle, the advantages such as the reaction time is fast, operating voltage is low, plate thickness is thin, thus there is wide development potentiality.

In order to improve the luminous efficiency of Organic Light Emitting Diode, the various luminescent material systems based on fluorescence and phosphorescence by It developed, have the characteristics that high reliablity using the Organic Light Emitting Diode of fluorescent material, but it is under electrical excitation in it Portion's electroluminescence quantum efficiency is restricted to 25%, this is because the singlet excited of exciton and the branching ratio of triplet excited state are 1:3.In contrast, almost 100% inside electroluminescent amount is had been achieved for using the Organic Light Emitting Diode of phosphor material Sub- efficiency.Theoretically, compared with fluorescent material, the luminous efficiency of phosphor material can be promoted to 4 times, therefore phosphorescence shines The exploitation of material has been widely studied.

Luminescent material (object) can be used as together luminescent material with host material (main body) to improve colour purity, shine and imitate Rate and stability.Since when using luminescent layer of the material of main part/object system as luminescent device, material of main part is to electroluminescent hair Efficiency and the characteristic influence of optical device are very big, therefore the selection of material of main part is critically important.

Currently, 4,4 '-two carbazoles-biphenyl (CBP) is the known host material for being most used as phosphorus extensively.In recent years Come, Japan Pioneer Co., Ltd (Pioneer) etc. develops a kind of high performance electroluminescent organic device, uses BAlq (two (2- first Base) -8-hydroxyquinoline conjunction -4- phenylphenol aluminium (III)), the compounds such as phenanthroline (BCP) are as matrix.

In current material design, people tend to carry out group using containing electron transporting groups and cavity transmission group Close, be designed to the main body of bipolar transmission, be beneficial to charge transmission balance, as patent US2016329506, Described in US20170170409 etc., or the derivative of one kind triazine or pyrimidine as disclosed in patent CN104541576A.Using bipolar Property transmission molecule do main body, good device performance can be obtained.But device performance obtained and service life are still to be improved.

Therefore, the prior art, especially material of main part solution have yet to be improved and developed.

Summary of the invention

Based on this, it is necessary to the organic optical compounds of one kind carbazoles containing naphthalene, mixture, composition and application thereof are provided, it should The organic optical compounds of class, mixture and composition are able to solve that existing phosphorescent light-emitting materials are at high cost, efficiency is rolled under high brightness The problem that drop is fast, the service life is short, and solve the problems, such as that TADF luminous organic material luminous efficiency is low and the service life is short.

Technical scheme is as follows:

A kind of organic compound of carbazoles containing naphthalene, has the structure as shown in structural formula (1-1) or structural formula (1-2):

Wherein:

Ar₁、Ar₂It is each independently selected from substitution or the unsubstituted aryl or heteroaryl for there are 5 to 30 annular atoms, Either selected from substitution or the unsubstituted non-aromatic ring group for having 5 to 30 annular atoms；

R₁、R₂It is each independently selected from H, D, the straight chained alkyl with 1 to 20 C atom, the alkane with 1 to 20 C atom Oxygroup, the thio alkoxy with 1 to 20 C atom, the branch with 3 to 20 C atoms or cricoid alkyl, have 3 to The branch or cricoid alkoxy, branch or cricoid thio alkoxy, monosilane with 3 to 20 C atoms of 20 C atoms Base, the ketone group with 1 to 20 C atom, the alkoxy carbonyl with 2 to 20 C atoms, the fragrant oxygen with 7 to 20 C atoms Base carbonyl, cyano, carbamoyl, halogen formoxyl, formoxyl, isocyano group, isocyanate group, thiocyanate groups, isothiocyanic acid Ester group, hydroxyl, nitro, CF₃, Cl, Br, F, crosslinkable group, the substituted or unsubstituted fragrance with 5 to 30 annular atoms Group or miscellaneous aromatic group, aryloxy group or heteroaryloxy group with 5 to 30 annular atoms；

A is 1,2,3 or 4；

B is 1,2,3,4,5 or 6；

When there are multiple R₁When, multiple R₁It is same or different to each other；When there are multiple R₂When, multiple R₂It is mutually the same or not Together；

Each Z₁Independently selected from CR₃Or N, at least one Z₁For N；R₃The same R of definition₁And R₂。

A kind of high polymer of carbazoles containing naphthalene, the repetitive unit of the high polymer of carbazoles containing naphthalene include above-mentioned organic compound Structure.

A kind of mixture of carbazoles containing naphthalene, including above-mentioned carbazoles containing naphthalene organic compound or above-mentioned carbazoles containing naphthalene height gather Object, and at least one organic functional material；The organic functional material is hole-injecting material, hole mobile material, electronics biography Defeated material, electron injection material, electron-blocking materials, hole barrier materials, illuminator or material of main part.

A kind of composition of carbazoles containing naphthalene, including above-mentioned carbazoles containing naphthalene organic compound or above-mentioned carbazoles containing naphthalene height gather Object, and at least one organic solvent.

The above-mentioned organic compound of carbazoles containing naphthalene, the high polymer of carbazoles containing naphthalene, the mixture of carbazoles containing naphthalene are in organic electronic Application in device.

A kind of organic electronic device includes at least a kind of organic compound of carbazoles containing naphthalene, carbazole containing naphthalene as described above Class high polymer, the mixture of carbazoles containing naphthalene.

A kind of organic electronic device, including luminescent layer, the luminescent layer contain the above-mentioned organic compound of carbazoles containing naphthalene, on State one of the high polymer of carbazoles containing naphthalene and above-mentioned carbazoles containing naphthalene mixture or a variety of.

The above-mentioned organic compound of carbazoles containing naphthalene, the high polymer of carbazoles containing naphthalene and the mixture of carbazoles containing naphthalene can be used as main body Material can improve it as electroluminescent device by cooperating with suitable object especially phosphorescent guest or TADF illuminator Luminous efficiency and the service life, provide that a kind of manufacturing cost is low, high-efficient, the service life is long, the solution party of the low luminescent device to roll-off Case.In addition, arranging in pairs or groups to form total main body with another main body with hole transporting property or with bipolarity property, can obtain further The electroluminescent efficiency of promotion and device lifetime.

Specific embodiment

The present invention provides the organic optical compounds of one kind carbazoles containing naphthalene, mixture, composition and application thereof, to make the present invention Purpose, technical solution and effect it is clearer, clear, the present invention is described in more detail below.It should be appreciated that this place The specific embodiment of description is only used to explain the present invention, is not intended to limit the present invention.

In the present invention, " D " and " D-atom " in substituent group has the same meaning, and can be interchanged between them.

In the present invention, composition and printing ink or ink have the same meaning, and can be interchanged between them.

In the present invention, material of main part, host material, Host or Matrix material have the same meaning, between them It can be interchanged.

In the present invention, HOMO indicates that highest occupied molecular orbital, LUMO indicate lowest unoccupied molecular orbital.

In the present invention, triplet can on table for E_T1, T1, T₁, they have the same meaning.

In the present invention, " substitution " indicates that the hydrogen atom being substituted in base is substituted replaced base.

In the present invention, structural compounds obtained from " annular atom number " indicates atomistic binding circlewise are (for example, monocycle Close object, fused ring compound, cross-linking compounds, carbocyclic compound, heterocyclic compound) composition the ring itself atom among original Subnumber.When the ring is substituted replaced base, the atom that substituent group is included does not include in ring member nitrogen atoms.About as described below " annular atom number " is also same under conditions of being not particularly illustrated.For example, the annular atom number of phenyl ring is 6, the ring of naphthalene nucleus is former Subnumber is 10, and the annular atom number of thienyl is 5.

In embodiments of the present invention, the level structure of organic material, triplet E_T1, HOMO, LUMO play it is crucial Effect.These energy levels customized one are introduced really below.

HOMO and lumo energy can be measured by photoelectric effect, for example, XPS (x-ray photoelectron spectroscopy) and UPS (ultraviolet photoelectron spectroscopy) passes through cyclic voltammetry (hereinafter referred to as CV).Recently, quantum chemical methods, such as density are general Letter theory (hereinafter referred to as DFT) also becomes the effective method for calculating molecular orbital energy level.

The triplet E of organic material_T1It can be measured by low temperature time- resolved emission spectrometry, or pass through quantum simulation It calculates and is obtained (as passed through Time-dependent DFT), such as pass through business software Gaussian 03W (Gaussian Inc.), It is described in embodiment that specific analogy method can be found in WO2011141110 or following.

It should be noted that HOMO, LUMO, E_T1Absolute value depend on measurement method or calculation method used, even for Identical method, the method for different evaluation, such as starting point and peak dot can provide different HOMO/LUMO values on CV curve. Therefore, rationally significant comparison should be carried out with identical measurement method and identical evaluation method.The embodiment of the present invention In description, HOMO, LUMO, E_T1Value be the simulation based on Time-dependent DFT, but do not influence other measurement or calculate The application of method.

In invention, (HOMO-1) is defined as the second high occupied orbital energy level, (HOMO-2) be third it is high occupy rail Road energy level, and so on.(LUMO+1) be defined as next to the lowest non-occupied orbital energy level, (LUMO+2) be third it is low occupy rail Road energy level, and so on.

In invention, in substituent groupIndicate the connection site of the substituent group, such as:Indicate dibenzofurans Optional position replaces on ring.

The present invention provides a kind of organic compound of carbazoles containing naphthalene as shown in structural formula (1-1) or (1-2):

Wherein:

R₁、R₂It is each independently selected from H, D, the straight chained alkyl with 1 to 20 C atom, the alkane with 1 to 20 C atom Oxygroup, the thio alkoxy with 1 to 20 C atom, the branch with 3 to 20 C atoms or cricoid alkyl, have 3 to The branch or cricoid alkoxy, branch or cricoid thio alkoxy, monosilane with 3 to 20 C atoms of 20 C atoms Base, the ketone group with 1 to 20 C atom, the alkoxy carbonyl with 2 to 20 C atoms, the fragrant oxygen with 7 to 20 C atoms Base carbonyl, cyano, carbamoyl, halogen formoxyl, formoxyl, isocyano group, isocyanate group, thiocyanate groups, isothiocyanic acid Ester group, hydroxyl, nitro, CF₃, Cl, Br, F, crosslinkable group, the substituted or unsubstituted fragrance with 5 to 30 annular atoms The combination of group or miscellaneous aromatic group, aryloxy group or heteroaryloxy group or these systems with 5 to 30 annular atoms；

A is 1,2,3 or 4；

B is 1,2,3,4,5 or 6；

Wherein, a indicates R on phenyl ring₁The number of substituent group, b indicate R on naphthalene nucleus₂The number of substituent group；

In certain preferred embodiments, two Z₁It is all N.

In a preferred embodiment, R₁、R₂It is each independently selected from H, D, the straight chain alkane with 1 to 20 C atom Base, the alkoxy with 1 to 10 C atom, the thio alkoxy with 1 to 10 C atom, the branch with 3 to 10 C atoms Chain or cricoid alkyl, the branch with 3 to 10 C atoms or cricoid alkoxy, the branch with 3 to 10 C atoms or Cricoid thio alkoxy, silicyl, the ketone group with 1 to 10 C atom, the alkoxy carbonyl with 2 to 10 C atoms Base, the aryloxycarbonyl with 7 to 10 C atoms, cyano, carbamoyl, halogen formoxyl, formoxyl, isocyano group, isocyanic acid Ester group, thiocyanate groups, isothiocyanate group, hydroxyl, nitro, CF₃, Cl, Br, F, crosslinkable group, have 5 to 30 rings Substituted or unsubstituted aromatic group or miscellaneous aromatic group, the aryloxy group or heteroaryloxy with 5 to 30 annular atoms of atom The combination of group or these systems.

Aromatic group refers to the alkyl for containing at least one aromatic ring, including monocyclic groups and polycyclic loop system.Heteroaromatic base Group refers to the alkyl (containing hetero atom) comprising at least one hetero-aromatic ring, including monocyclic groups and polycyclic loop system.These are polycyclic Ring can have two or more rings, two of them carbon atom is shared by two adjacent rings, i.e. condensed ring.These polycyclic rings Kind, at least one is aromatics or heteroaromatic.Hetero atom in heteroaromatic is preferably selected from Si, N, P, O, S and/or Ge, especially It is preferably selected from Si, N, P, O and/or S.For the purpose of the present invention, aromatic series or heteroaromatic group not only include aromatic radical or The system of heteroaryl perfume base, moreover, plurality of aryl or heteroaryl can also be interrupted (such as < 10% by short non-aromatic unit Non- H atom, 5% non-H atom, such as C, N or O atom)., two fluorenes of 9'- spiral shell, 9,9- diaryl fluorenes, three virtues Amine, the systems such as diaryl ether, for the goal of the invention it also hold that being aromatic group.

Specifically, the preferred example of aromatic group has: benzene, naphthalene, anthracene, phenanthrene, perylene, aphthacene, pyrene, BaP, three Sub- benzene, acenaphthene, fluorenes and its derivative.

Specifically, the preferred example of heteroaromatic group has: furans, benzofuran, thiophene, benzothiophene, pyrroles, pyrazoles, Triazole, imidazoles, oxazole, oxadiazoles, thiazole, tetrazolium, indoles, carbazole, pyrrolo- imidazoles, pyrrolopyrrole, Thienopyrroles, thiophene Pheno bithiophene, furans and pyrroles, furans and furans, thienofuran, benzo isoxazole, benzisothiazole, benzimidazole, pyrrole Pyridine, pyrazine, pyridazine, pyrimidine, triazine, quinoline, isoquinolin, cinnoline, quinoxaline, phenanthridines, primary pyridine, quinazoline, quinazolinone, And its derivative.

Further, for the purpose of the present invention, substituent R₁、R₂It is optional in (1) C1~C10 alkyl particularly preferably refers to Following group: methyl, ethyl, n-propyl, isopropyl, cyclopropyl, normal-butyl, isobutyl group, sec-butyl, tert-butyl, cyclobutyl, 2- methyl butyl, n-pentyl, n-hexyl, cyclohexyl, n-heptyl, suberyl, n-octyl, cyclooctyl, 2- ethylhexyl, fluoroform Base, five methyl fluorides, 2,2,2- trifluoroethyl, vinyl, acrylic, cyclobutenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexene Base, heptenyl, cycloheptenyl, octenyl, cyclo-octene base, acetenyl, propinyl, butynyl, pentynyl, hexin base and octyne Base；(2) C1~C10 alkoxy, particularly preferably nail oxygroup, ethyoxyl, positive propoxy, isopropoxy, n-butoxy are different Butoxy, sec-butoxy, tert-butoxy or 2- methyl butoxy；(3) C2 to C10 aryl or heteroaryl, depend on purposes its It can be monovalence or divalent, it in each case can also be by the above-mentioned group R referred to³Replace and any hope can be passed through Position connect with aromatic series or miscellaneous aromatic rings, it is particularly preferred to refer to group below: benzene, naphthalene, anthracene, pyrene, dihydropyrene, It bends, Asia puecon, firefly anthracene, naphthacene, pentacene, BaP, furans, benzofuran, isobenzofuran, dibenzofurans, thiophene, benzo thiophene Pheno, isothiophene, dibenzothiophen, pyrroles, indoles, iso-indoles, carbazole, pyridine, quinoline, isoquinolin, acridine, phenanthridines, benzo -5,6- Quinoline, benzo -6,7- quinoline, benzo -7,8- quinoline, phenthazine, phenoxazine, pyrazoles, indazole, imidazoles, benzimidazole, naphtho- miaow Azoles, phenanthro- imidazoles, pyridine-imidazole, pyrazine and imidazoles, quinoxaline and imidazoles, oxazole, benzoxazoles, aphthoxazoles, anthra evil Azoles, phenanthro- oxazole, isoxazole, 1,2- thiazole, 1,3- thiazole, benzothiazole, pyridazine, benzo pyridazine, pyrimidine, benzo pyrimidine, quinoline Quinoline, pyrazine, phenazine, 1,5- benzodiazine, nitrogen carbazole, benzo carboline, phenanthroline, 1,2,3- triazole, 1,2,4- triazole, benzene And triazole, 1,2,3- oxadiazoles, 1,2,4- oxadiazoles, 1,2,5- oxadiazoles, 1,3,4- oxadiazoles, 1,2,3- thiadiazoles, 1,2, 4- thiadiazoles, 1,2,5- thiadiazoles, 1,3,4- thiadiazoles, 1,3,5- triazine, 1,2,4- triazine, 1,2,3- triazine, tetrazolium.1,2, 4,5- tetrazine, 1,2,3,4- tetrazine, 1,2,3,5- tetrazine, purine, pteridine, indolizine and diazosulfide.For of the invention Purpose, fragrant and heteroaromatic ring system also refer to biphenylene, sub- terphenyl, fluorenes, spiral shell in addition to the above-mentioned aryl and heteroaryl referred to Two fluorenes, dihydro phenanthrene, tetrahydro pyrene and cis or trans indenofluorene.

In a preferred embodiment, organic compound according to the invention, the Ar₁、Ar₂Selected from 5 to 30 rings The aryl or heteroaryl of atom；In one more preferably embodiment, the Ar₁、Ar₂Virtue selected from 5 to 25 annular atoms Base or heteroaryl；In a preferred embodiment, the Ar₁、Ar₂Aryl or miscellaneous selected from 6 to 20 annular atoms Aryl；

In a preferred embodiment, organic compound according to the invention, the Ar₁、Ar₂For at least one Such as the group of flowering structure:

Wherein:

When having multiple in same group, each X is each independently selected from N or CR₅；

When having multiple in same group, each Y is each independently selected from CR₆R₇, SiR₆R₇, NR₆Or, C (=O), S,

Or O；

R₅、R₆、R₇The same R of meaning₁；

Further, organic compound according to the invention, the Ar₁、Ar₂It can be selected from following building stone One or more combinations, they further can arbitrarily be replaced:

In further some embodiments, according to structural formula (1-1) or the compound of structural formula (1-2), wherein Ar₁,Ar₂Include following structural unit or their combination with may be the same or different when repeatedly occurring:

Wherein n is 1,2,3 or 4.

In certain preferential embodiments, (S1-T1)≤0.3eV of the organic compound of carbazoles containing naphthalene, preferably ≤ 0.25eV, more preferably≤0.2eV, preferably≤0.10eV.

In other preferential embodiments, Ar in the above-mentioned organic compound of carbazoles containing naphthalene₂It include an electron-donating group Group.Suitable electron-donating group can be selected from include following group structure:

In one embodiment, Ar₁、Ar₂It is each independently selected from following group:

Wherein, A O, S, N-Ph or CR₈R₉, R₈、R₉It is each independently C1-C6 alkyl.

In one embodiment, R₈For methyl, R₉For methyl.

The above-mentioned organic compound of carbazoles containing naphthalene can be used as functional material in electronic device.Organic functional material can It is divided into hole-injecting material (HIM), hole mobile material (HTM), electron transport material (ETM), electron injection material (EIM), Electron-blocking materials (EBM), hole barrier materials (HBM), illuminator (Emitter), material of main part (Host).Preferably at one Embodiment in, the above-mentioned organic compound of carbazoles containing naphthalene can be used as material of main part, electron transport material or hole mobile material. In a more preferred embodiment, the above-mentioned organic compound of carbazoles containing naphthalene is as phosphorescent light body material.

Must there are triplet appropriate, i.e. E as phosphorescent light body material_T1.In certain embodiments, above-mentioned click containing naphthalene The E of azole organic compound_T1>=2.3eV, preferably >=2.4eV, more preferable >=2.5eV, more more preferably >=2.6eV, best >=2.7eV.

As phosphorescent light body material, it is hoped that there will be good thermal stability.In one embodiment, above-mentioned carbazoles containing naphthalene organises Glass transition temperature Tg >=100 DEG C of object are closed, in a preferred embodiment, Tg >=120 DEG C, in a more preferred implementation In example, Tg >=140 DEG C, in a particularly preferred embodiment, Tg >=160 DEG C, in a highly preferred embodiment, Tg ≥180℃。

In certain preferential embodiments, the above-mentioned organic compound of carbazoles containing naphthalene ((HOMO- (HOMO-1)) >= 0.2eV, preferably >=0.25eV, more preferably >=0.3eV, more more preferably >=0.35eV, very good is >=0.4eV, preferably >= 0.45eV。

In other preferential embodiments, the above-mentioned organic compound of carbazoles containing naphthalene (((LUMO+1)-LUMO) >= 0.15eV, preferably >=0.20eV, more preferably >=0.25eV, more more preferably >=0.30eV, preferably >=0.35eV.

In certain embodiments, the above-mentioned organic compound of carbazoles containing naphthalene has light-emitting function, and emission wavelength is arrived 300 Between 1000nm, preferably 350 between 900nm, more preferably 400 between 800nm.Herein refer to it is luminous refer to it is photic Luminous or electroluminescent.

In a preferred embodiment, the above-mentioned organic compound of carbazoles containing naphthalene preferably is selected from but is not limited to such as flowering structure, These structures can arbitrarily be replaced.

The present invention is further directed to a kind of high polymer of carbazoles containing naphthalene, the repetitive unit of the high polymer of carbazoles containing naphthalene Structure comprising the above-mentioned organic compound of carbazoles containing naphthalene.

In a preferred embodiment, the synthetic method of the above-mentioned high polymer of carbazoles containing naphthalene is selected from SUZUKI-, YAMAMOTO-,STILLE-,NIGESHI-,KUMADA-,HECK-,SONOGASHIRA-,HIYAMA-,FUKUYAMA-, HARTWIG-BUCHWALD- and ULLMAN.

In a preferential embodiment, the glass transition temperature (Tg) >=100 DEG C of the above-mentioned high polymer of carbazoles containing naphthalene, preferably It is >=120 DEG C, more excellent is >=140 DEG C, and more excellent is >=160 DEG C, and optimal is >=180 DEG C.

In a preferential embodiment, molecular weight distribution (PDI) value range of the above-mentioned high polymer of carbazoles containing naphthalene is excellent It is selected as 1~5；It is more preferably 1~4；More preferably 1~3, yet more preferably 1~2, most preferably 1~1.5.

In a preferential embodiment, weight average molecular weight (Mw) value range of the above-mentioned high polymer of carbazoles containing naphthalene is preferred It is 10,000~1,000,000；It is more preferably 50,000~500,000；More preferably 100,000~400,000, yet more preferably 150,000~300,000, most preferably It is 200,000~250,000.

The invention further relates to a kind of mixtures of carbazoles containing naphthalene, have including above-mentioned organic compound and at least one Machine functional material.The organic functional material, including hole (also referred to as electric hole) injection or transmission material (HIM/HTM), hole resistance Obstructing material (HBM), electron injection or transmission material (EIM/ETM), electron-blocking materials (EBM), organic host material (Host), Singlet emitters (fluorescent illuminant), weight state illuminator (phosphorescent emitter), especially luminescent organometallic complex compound, and have Machine thermal excitation delayed fluorescence material (TADF material).Such as in WO2010135519A1, US20090134784A1 and Various organic functional materials are described later in detail in WO2011110277A1, hereby by the full content in this 3 patent document It is incorporated herein by reference.Organic functional material can be small molecule and high polymer material.

In certain embodiments, the mixture of carbazoles containing naphthalene include at least one above-mentioned organic compound of carbazoles containing naphthalene or The high polymer of carbazoles containing naphthalene and a kind of fluorescent illuminant.Here the organic compound of carbazoles containing naphthalene or the high polymer of carbazoles containing naphthalene are made For fluorescent host material, wherein the fluorescent illuminant weight percent is≤10wt%, preferably≤9wt%, more preferably ≤ 8wt%, particularly preferably≤7wt%, preferably≤5wt%.

In a particularly preferred embodiment, the mixture of carbazoles containing naphthalene includes at least one above-mentioned carbazole containing naphthalene Class organic compound or the high polymer of carbazoles containing naphthalene and a kind of phosphorescent emitter.Here the organic compound of carbazoles containing naphthalene or contain naphthalene Carbazoles high polymer is as phosphorescent light body material, wherein the phosphorescent emitter weight percent is≤25wt%, preferably ≤ 20wt%, more preferably≤15wt%.

In another preferred embodiment, the mixture of carbazoles containing naphthalene includes at least one above-mentioned carbazoles containing naphthalene Organic compound or the high polymer of carbazoles containing naphthalene, a kind of phosphorescent emitter and the second material of main part.In such an embodiment, above-mentioned The organic compound of carbazoles containing naphthalene or the high polymer of carbazoles containing naphthalene as auxiliary light emission material, with phosphorescent emitter weight ratio from 1:2 to 2:1.In another preferred embodiment, the above-mentioned organic compound of carbazoles containing naphthalene or the high polymer of carbazoles containing naphthalene with Second material of main part forms exciplex, and the energy level of the exciplex is higher than the phosphorescent emitter.

In another preferred embodiment, the mixture of carbazoles containing naphthalene includes at least one above-mentioned carbazoles containing naphthalene Organic compound or the high polymer of carbazoles containing naphthalene and a kind of TADF material.Here the organic compound of carbazoles containing naphthalene or click containing naphthalene Material of main part of the azole high polymer as TADF luminescent material, wherein the weight percent of the TADF material be≤ 15wt%, preferably≤10wt%, more preferably≤8wt%.

In a highly preferred embodiment, the mixture of carbazoles containing naphthalene includes at least one above-mentioned carbazole containing naphthalene Class organic compound or the high polymer of carbazoles containing naphthalene and the second material of main part.Here organic compound according to the invention can be with As the first main body, weight percent can be 30%~70%, preferably 40%~60%.

In certain especially preferential embodiments, second material of main part has structure shown in structural formula (2):

Wherein, Ar₃,Ar₄It is each independently selected from substitution or the unsubstituted aryl for there are 5 to 30 annular atoms or miscellaneous Aryl, either selected from substitution or the unsubstituted non-aromatic ring group for having 5 to 30 annular atoms.

Preferably, the second material of main part can be selected from the compound with structure below, and the compound of following structures can Further arbitrarily to be replaced.

Below to fluorescence luminescent material or singlet emitters, phosphorescent light-emitting materials or triplet emitters and TADF material Material makees some more detailed descriptions (but not limited to this).

1. singlet emitters (Singlet Emitter)

Singlet emitters often have longer conjugated pi electron system.So far, there are many examples, such as Styrylamine disclosed in JP2913116B and WO2001021729A1 and its derivative, in WO2008/006449 and WO2007/ The triaryl amine of indenofluorene and its derivative disclosed in 140847 and the pyrene disclosed in US7233019, KR2006-0006760 Derivative.

In a preferential embodiment, singlet emitters can be selected from unitary styrylamine, binary styrylamine, and three First styrylamine, quaternary styrylamine, styrene phosphine, styrene ether and arylamine.

One unitary styrylamine refers to a compound, it is comprising unsubstituted or substitution a styryl group and at least One amine, preferably aromatic amine.One binary styrylamine refers to a compound, it includes two benzene second that are unsubstituted or replacing Alkenyl group and at least one amine, preferably aromatic amine.One ternary styrylamine refers to a compound, it includes three unsubstituted Or the styryl group and at least one amine, preferably aromatic amine replaced.One quaternary styrylamine refers to a compound, it is wrapped Containing four styryl groups and at least one amine, preferably aromatic amine unsubstituted or replace.One preferred styrene is two Styrene may be further substituted.The definition of corresponding phosphine and ethers is similar to amine.Arylamine or aromatic amine are Refer to a kind of compound, the aromatic rings or heterocyclic ring system for directly coupling the unsubstituted of nitrogen comprising three or replacing.These aromatic series or At least one in the loop system of heterocycle is preferentially selected in fused ring system, and is preferably formed at least 14 aromatic ring atoms.Wherein preferably Example have a fragrant anthranylamine, fragrant anthradiamine, fragrant pyrene amine, fragrant pyrene diamines, fragrance amine in the wrong and fragrance diamines in the wrong.One fragrance Anthranylamine refers to a compound, and one of binary arylamine group is directly linked on anthracene, preferably on 9 position.One virtue Fragrant anthradiamine refers to a compound, and wherein two binary arylamine group is directly linked on anthracene, preferably on 9,10 position. Fragrant pyrene amine, fragrant pyrene diamines, fragrance amine in the wrong is similar with the fragrance definition of diamines in the wrong, and wherein binary arylamine group is preferably linked to On 1 or 1,6 positions of pyrene

The example of singlet emitters based on vinylamine and arylamine, and preferred example, can be in following patent documents In find: WO 2006/000388, WO 2006/058737, WO 2006/000389, WO 2007/065549, WO 2007/ 115610,US 7250532 B2,DE 102005058557 A1,CN 1583691 A,JP 08053397 A,US 6251531 B1, US 1957606 A1 of 2006/210830 A, EP and 2008/0113101 A1 of US are hereby in the above-mentioned patent document listed Full content be incorporated herein by reference.

The example of singlet emitters based on stibene extremely derivative has US 5121029.

Further preferred singlet emitters are optional in indenofluorene-amine and indenofluorene-diamines, such as WO 2006/ Disclosed in 122630, benzo indenofluorene-amine and benzo indenofluorene-diamines, as disclosed in WO 2008/006449, dibenzo Indenofluorene-amine and dibenzo indenofluorene-diamines, as disclosed in WO2007/140847.

Further preferred singlet emitters are optional in the fused ring system based on fluorenes, as US2015333277A1, Disclosed in US2016099411A1, US2016204355A1.

The optional derivative in pyrene of more preferred singlet emitters, the structure as disclosed in US2013175509A1； The triarylamine derivative of pyrene, the triarylamine derivative of the pyrene containing dibenzofurans unit as disclosed in CN102232068B； The triarylamine derivative of other pyrenes with specific structure, as disclosed in CN105085334A, CN105037173A.Other can Material as singlet emitters has polycyclic aromatic hydrocarbon compounds, the derivative of especially following compound: anthracene such as 9,10- bis- (2- naphthanthracene), naphthalene, four benzene, xanthene is luxuriant and rich with fragrance, and pyrene (such as 2,5,8,11- tetra--t- butyl), indeno pyrene, penylene is as (4,4 '-is bis- (9- ethyl -3- carbazole vinyl) -1,1 '-biphenyl), two indeno pyrenes, decacyclene, coronene, fluorenes, two fluorenes of spiral shell, aryl pyrene is (such as US20060222886), arylene ethylene (such as US5121029, US5130603), cyclopentadiene such as tetraphenyl cyclopentadiene, Rubrene, cumarin, rhodamine, quinacridone, (4- is to dimethylaminostyryl-by pyrans such as 4 (dicyano methylene) -6- 2- methyl) -4H- pyrans (DCM), thiapyran, bis- (azine) imines boron compounds (2007/0092753 A1 of US), bis- (azines Base) methylene compound, carbostyryl compound, oxazinone, benzoxazoles, benzothiazole, benzimidazole and pyrrolo- pyrrole Cough up diketone.The material of some singlet emitters can be found in following patent documents: US 20070252517 A1, US 4769292,US 6020078,US 2007/0252517 A1,US 2007/0252517 A1.Hereby by the above-mentioned patent listed Full content in file is incorporated herein by reference.

The example of some suitable singlet emitters is listed in following table:

2. triplet emitters (Triplet Emitter)

Triplet emitters are also referred to as phosphorescent emitter.In a preferential embodiment, triplet emitters are that have knot The metal complex of structure formula M (L) n, wherein M is a metallic atom, can be identical or different when L occurs every time, is one organic Ligand, it passes through, and one or more positions are bonded or coordination is connected on metallic atom M, and n is an integer greater than 1, preferably Choosing is 1,2,3,4,5 or 6.Optionally, these metal complexes are connected on a polymer by one or more positions, most It is well to pass through organic ligand.

In a preferential embodiment, metallic atom M is selected in transition metal element or lanthanide series or actinides, Preferential selection Ir, Pt, Pd, Au, Rh, Ru, Os, Sm, Eu, Gd, Tb, Dy, Re, Cu or Ag, especially preferentially selection Os, Ir, Ru, Rh, Re, Pd, Au or Pt.

Preferentially, triplet emitters include cheland, i.e. ligand, are matched by least two binding sites with metal Position, what is given special priority for be triplet emitters includes two or three identical or different bidentates or multidentate ligand.Chela Close the stability that ligand is conducive to improve metal complex.

The example of organic ligand can be selected from phenylpyridine derivative, 7,8- benzoquinoline derivatives, 2 (2- thienyl) pyridines Derivative, 2 (1- naphthalene) pyridine derivates or 2 phenylchinoline derivatives.All these organic ligands may be all substituted, example Such as replaced by fluorine-containing or trifluoromethyl.Assistant ligand can be preferably selected from acetic acid acetone or picric acid.

In a preferential embodiment, the metal complex that can be used as triplet emitters has following form:

Wherein M is a metal, is selected in transition metal element or group of the lanthanides or actinides, that especially preferential is Ir, Pt, Au；

Ar₁It can be when occurring every time identical or different, be a cyclic group, wherein at least include alms giver's original Son has the atom of a lone pair electrons, such as nitrogen or phosphorus, connected by its cyclic group and metal coordination；Ar₂It can when occurring every time It is a cyclic group to be identical or different, wherein at least includes a C atom, is connected by its cyclic group and metal It connects；Ar₁And Ar₂It is linked together by covalent bond, can respectively carry one or more substituent groups, they can also pass through substitution again Group is linked together；L ' can be when occurring identical or different every time, be the assistant ligand of bidentate chelating, preferably singly Anion double-tooth chelate ligand；X can be 0,1,2 or 3, be preferentially 2 or 3；Y can be 0,1,2 or 3, be preferentially 1 or 0.

The example that the material of some triplet emitters is extremely applied can be found in following patent documents and document: 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 2010102709,US 20070087219 A1,US 20090061681 A1,US 20010053462 A1,Baldo,Thompson et al.Nature 403,(2000),750-753,US 20090061681 A1,US 20090061681 A1,Adachi et al.Appl.Phys.Lett.78(2001),1622-1624,J.Kido et al.Appl.Phys.Lett.65(1994),2124,Kido et al.Chem.Lett.657,1990,US 2007/0252517 A1,Johnson et al.,JACS105,1983,1795,Wrighton,JACS 96,1974,998,Ma et al., Synth.Metals 94,1998,245,US 6824895,US 7029766,US 6835469,US 6830828,US 20010053462 A1,WO 2007095118 A1,US 2012004407A1,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,WO2014023377A1.The full content in the above-mentioned patent document and document listed is incorporated to hereby Herein as reference.

The example of some suitable triplet emitters is listed in following table:

3. hot activation delayed fluorescence luminescent material (TADF):

Traditional organic fluorescence materials can only be shone using 25% singlet exciton to be formed is electrically excited, the interior quantum effect of device Rate is lower (up to 25%).Although phosphor material passes through between being since the strong SO coupling in heavy atom center enhances, It can efficiently use and be electrically excited the singlet exciton to be formed and Triplet exciton, reach the internal quantum efficiency of device 100%.But phosphor material is expensive, and stability of material is poor, and device efficiency the problems such as serious of roll-offing limits its answering in OLED With.Hot activation delayed fluorescence luminescent material is the organic hair of the third generation developed after organic fluorescence materials and organic phosphorescent material Luminescent material.Such material generally has poor (the Δ E of small singlet-triplet_st), triplet excitons can by it is counter be between Pass through be transformed into singlet exciton shine.This can make full use of the singlet exciton and triplet excitons that are electrically excited lower formation. Device internal quantum efficiency can reach 100%.Material structure is controllable simultaneously, and property is stablized, cheap woth no need to noble metal, The field OLED has a extensive future.

TADF material needs to have lesser singlet-triplet poor, preferably Δ Est < 0.3eV, and secondary is well Δ Est < 0.25eV, more preferably Δ Est < 0.20eV, preferably Δ Est < 0.1eV.In a preferential embodiment, TADF material Material has smaller Δ Est, and in another preferential embodiment, TADF has preferable fluorescence quantum efficiency.Some TADF Luminous material can be found in following 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.al.Appl.Phys.Lett., 101,2012, 093306, Adachi, et.al.Chem.Commun., 48,2012,11392, Adachi, et.al.Nature Photonics, 6,2012,253, Adachi, et.al.Nature, 492,2012,234, Adachi, et.al.J.Am.Chem.Soc, 134, 2012,14706, Adachi, et.al.Angew.Chem.Int.Ed, 51,2012,11311, Adachi, Et.al.Chem.Commun., 48,2012,9580, Adachi, et.al.Chem.Commun., 48,2013,10385, Adachi, et.al.Adv.Mater., 25,2013,3319, Adachi, et.al.Adv.Mater., 25,2013,3707, Adachi, et.al.Chem.Mater., 25,2013,3038, Adachi, et.al.Chem.Mater., 25,2013,3766, Adachi, et.al.J.Mater.Chem.C., 1,2013,4599, Adachi, et.al.J.Phys.Chem.A., 117, 2013,5607, the full content in the above-mentioned patent listed or article file is incorporated herein by reference hereby.

It is an object of the invention to provide material solution for vapor deposition type OLED.

In certain embodiments, molecular weight≤1100g/mol of the above-mentioned organic compound of carbazoles containing naphthalene, preferably≤ 1000g/mol, very preferably≤950g/mol, more preferably≤900g/mol, most preferably≤800g/mol.

Another object of the present invention is to provide material solution for printing OLED.

In certain embodiments, the molecular weight >=700g/mol, preferably >=900g/ of the above-mentioned organic compound of carbazoles containing naphthalene Mol, very preferably >=900g/mol, more preferably >=1000g/mol, most preferably >=1100g/mol.

In further embodiments, above-mentioned carbazole compound containing naphthalene, at 25 DEG C, solubility in toluene >= 10mg/ml, preferably >=15mg/ml, most preferably >=20mg/ml.

The present invention is further directed to one kind composition of carbazoles containing naphthalene or ink, including at least one above-mentioned click containing naphthalene Azole organic compound or above-mentioned carbazoles containing naphthalene high polymer, and at least one organic solvent.

When for printing technology, the viscosity of ink, surface tension is important parameter.The surface tension ginseng of suitable ink Number is suitable for specific substrate and specific printing process.

In a preferred embodiment, ink according to the invention operating temperature or surface tension at 25 DEG C about In 19dyne/cm to 50dyne/cm range；More preferably in 22dyne/cm to 35dyne/cm range；Preferably in 25dyne/cm To 33dyne/cm range.

In another preferred embodiment, viscosity of the ink according to the invention at operating temperature or 25 DEG C about exists 1cps to 100cps range；Preferably in 1cps to 50cps range；More preferably in 1.5cps to 20cps range；Preferably exist 4.0cps to 20cps range.The composition so prepared will be convenient for ink jet printing.

Viscosity can be adjusted by different methods, as by suitable solvent choose and ink in functional material it is dense Degree.It is according to the invention include the ink of described ground metal organic complex or high polymer can facilitate people will print ink by It is adjusted according to printing process used in range appropriate.Generally, the weight for the functional material that composition according to the invention includes Amount ratio is 0.3%~30wt% range, is preferably 0.5%~20wt% range, is preferably 0.5%~15wt% range, It is more preferably 0.5%~10wt% range, it is best for 1%~5wt% range.

In some embodiments, ink according to the invention, at least one organic solvent, which is selected from, is based on aromatics Or heteroaromatic solvent, especially aliphatic chain/cyclosubstituted arsol or aromatics ketone solvent or aromatic ether solvents.

Being suitble to the example of solvent of the invention has, but is not limited to: based on aromatics or heteroaromatic solvent: to diisopropyl Benzene, penta benzene, naphthane, cyclohexyl benzene, chloronaphthalene, 1,4- dimethylnaphthalene, 3- isopropyl biphenyl, p-Methylisopropylbenzene, diamyl benzene, three Penta benzene, amyl toluene, ortho-xylene, meta-xylene, paraxylene, adjacent diethylbenzene, NSC 62102, p-Diethylbenzene, 1,2,3,4- It is durene, 1,2,3,5- durene, 1,2,4,5- durene, butylbenzene, detergent alkylate, dihexyl benzene, dibutyl benzene, different to two Propylbenzene, 1- methoxynaphthalene, cyclohexyl benzene, dimethylnaphthalene, 3- isopropyl biphenyl, p-Methylisopropylbenzene, 1- methyl naphthalene, 1,2,4- Trichloro-benzenes, 1,3- dipropoxy benzene, 4,4- difluoro-diphenylmethane, 1,2- dimethoxy-4 '-(1- acrylic) benzene, diphenyl-methane, 2- phenylpyridine, 3- phenylpyridine, N- methyldiphenylamine, 4- isopropyl biphenyl, dichloro diphenyl methane, 4- (3- phenyl propyl) pyrrole Bis- (3,4- 3,5-dimethylphenyl) ethane of pyridine, Ergol, 1,1-, 2- isopropyl naphthalene, benzyl ether etc.；Solvent based on ketone: 1- Tetralone, 2- tetralone, 2- (phenyl epoxy) tetralone, 6- (methoxyl group) tetralone, acetophenone, propiophenone, two Benzophenone and their derivative, as 4- methyl acetophenone, 3- methyl acetophenone, 2- methyl acetophenone, 4- methyl phenyl ketone, 3- methyl phenyl ketone, 2- methyl phenyl ketone, isophorone, 2,6,8- trimethyl -4- nonanones, fenchone, methyl n-heptyl ketone, 3- nonanone, 5- Nonanone, 2- decanone, 2,5- acetyl butyryl, phorone, two n-pentyl ketone；Aromatic ether solvents: 3- phenoxytoluene, butyl phenyl ether, benzyl Base butyl benzene, p-anisaldehyde dimethyl-acetal, tetrahydro -2- phenoxy group -2H- pyrans, 1,2- dimethoxy-4 '-(1- acrylic) Benzene, 1,4- benzdioxan, 1,3- dipropyl benzene, 2,5- dimethoxy-p, 4- ethyl this ether, 1,2,4- trimethoxy Benzene, 4- (1- acrylic) -1,2- dimethoxy benzene, 1,3- dimethoxy benzene, glycidyl phenyl ether, dibenzyl ether, uncle 4- Butyl anisole, trans--anethole, 1,2- dimethoxy benzene, 1- methoxynaphthalene, diphenyl ether, 2- phenoxy group methyl ether, 2- phenoxy group tetrahydrofuran, ethyl -2- naphthyl ether, amyl ether c hexyl ether, dioctyl ether, butyl cellosolve, diethylene glycol diethyl ether, Diethylene glycol butyl methyl ether, dibutyl ethylene glycol ether, triethylene glycol dimethyl ether, triethylene glycol ethyl methyl ether, triethylene glycol butyl Methyl ether, tripropylene glycol dimethyl ether, tetraethyleneglycol dimethyl ether；Ester solvent: sad alkyl ester, decanedioic acid alkyl ester, stearic acid alkyl ester, benzene first Sour alkyl ester, phenylacetic acid alkyl ester, cinnamic acid alkyl ester, oxalic acid alkyl ester, maleic acid alkyl ester, alkane lactone, oleic acid alkyl ester etc..

Further, ink according to the invention, described at least one have solvent can be selected from: aliphatic ketone, for example, 2- Nonanone, 3- nonanone, butyl ketone, 2- decanone, 2,5- acetyl butyryl, 2,6,8- trimethyl -4- nonanone, phorone, two n-pentyl ketone etc.； Or fatty ether, for example, amyl ether, hexyl ether, dioctyl ether, butyl cellosolve, diethylene glycol diethyl ether, diethylene glycol butyl first Ether, dibutyl ethylene glycol ether, triethylene glycol dimethyl ether, triethylene glycol ethyl methyl ether, triethylene glycol butyl methyl ether, tripropylene glycol two Methyl ether, tetraethyleneglycol dimethyl ether etc..

In further embodiments, the printing ink further includes another organic solvent.It is another organic The example of solvent includes but is not limited to: methanol, ethyl alcohol, 2-methyl cellosolve, methylene chloride, chloroform, chlorobenzene, adjacent dichloro Benzene, tetrahydrofuran, methyl phenyl ethers anisole, morpholine, toluene, ortho-xylene, meta-xylene, paraxylene, 1,4 dioxanes, acetone, Methyl ethyl ketone, 1,2 dichloroethanes, 3- phenoxytoluene, 1,1,1- trichloroethanes, 1,1,2,2- tetrachloroethanes, ethyl acetate, Butyl acetate, dimethylformamide, dimethyl acetamide, dimethyl sulfoxide, naphthane, naphthalane, indenes and/or their mixing Object.

In a preferred embodiment, the above-mentioned composition of carbazoles containing naphthalene is a solution.

In another preferred embodiment, the above-mentioned composition of carbazoles containing naphthalene is a suspension.

It may include that 0.01 to 20wt% carbazoles containing naphthalene according to the invention has in the above-mentioned composition of carbazoles containing naphthalene Machine compound or the mixture of carbazoles containing naphthalene, preferably 0.1 to 15wt%, preferably 0.2 to 10wt%, most preferably 0.25 to the 5wt% organic compound of carbazoles containing naphthalene or the mixture of carbazoles containing naphthalene.

The invention further relates to the composition of carbazoles containing naphthalene as coating or printing ink preparing organic electronic device When purposes, particularly preferably by printing or coating preparation method.

Wherein, suitable printing or coating technique include but is not limited to inkjet printing, spray printing (Nozzle Printing), roller printing, lithographic plate print are reversed in typographic printing, silk-screen printing, dip-coating, rotary coating, blade coating, roller printing Brush, flexographic printing, rotary printing, spraying, brushing or bat printing, slit-type squash type coating etc..It is preferred that ink jet printing, spray printing And intaglio printing.Solution or suspension can also comprise one or more components such as surface active cpd, lubricant, profit Humectant, dispersing agent, hydrophobing agent, bonding agent etc., for adjusting viscosity, filming performance improves adhesion etc..Related printing technique, And its to the related request in relation to solution, such as solvent and concentration, viscosity etc., details refer to Helmut Kipphan master " print media handbook: technology and production method " (the Handbook of Print Media:Technologies and compiled Production Methods),ISBN 3-540-67326-1。

Based on the above-mentioned organic compound of carbazoles containing naphthalene, the present invention also provides a kind of carbazoles containing naphthalene as described above to organise The application of object is closed, i.e., the organic compound of carbazoles containing naphthalene or the high polymer of carbazoles containing naphthalene are applied to organic electronic device, The organic electronic device is optional in but being not limited to, Organic Light Emitting Diode (OLED), organic photovoltaic battery (OPV) is organic Light emitting electrochemical cell (OLEEC), organic field-effect tube (OFET), organic light-emitting field effect pipe, organic laser, organic spinning electron device Part, organic sensor and organic phasmon emitting diode (Organic Plasmon Emitting Diode) etc., especially Preferably organic electroluminescence device, such as OLED, OLEEC, organic light-emitting field effect pipe.In the embodiment of the present invention, preferably will The organic compound is used for the luminescent layer of electroluminescent device.

The invention further relates to a kind of organic electronic devices, include at least a kind of organic compound as described above or height Polymers.In general, such organic electronic device contains at least one cathode, an anode and between cathode and anode one A functional layer, wherein including at least a kind of organic compound as described above or high polymer in the functional layer.Described has Machine electronic device is optional in but being not limited to, Organic Light Emitting Diode (OLED), organic photovoltaic battery (OPV), organic light emission battery (OLEEC), organic field-effect tube (OFET), organic light-emitting field effect pipe, organic laser, organic spin electric device are organic Sensor and organic phasmon emitting diode (Organic Plasmon Emitting Diode) etc., particularly preferably Organic electroluminescence device, such as OLED, OLEEC, organic light-emitting field effect pipe.

In certain especially preferential embodiments, the electroluminescent device, luminescent layer includes to have described in one kind Machine compound, or comprising organic compound described in one kind and a kind of phosphorescent emitter, or include organic compound described in one kind Object and a kind of material of main part, or include organic compound described in one kind, a kind of phosphorescent emitter and a kind of material of main part.

In above-described electroluminescent device, especially OLED, including a substrate, an anode, at least a luminescent layer, One cathode.

Substrate can be opaque or transparent.One transparent substrate can be used to manufacture a transparent luminous first device Part.It see, for example, the Nature such as Bulovic 1996,380, p29 and Gu etc., Appl.Phys.Lett.1996,68, p2606.Substrate can be rigid or elasticity.Substrate can be plastics, metal, semiconductor wafer or glass.Preferably base Piece has a smooth surface.Substrate free of surface defects is especially desirable selection.In a preferred embodiment, substrate It is flexible, optional in thin polymer film or plastics, glass transition temperature Tg is 150 DEG C or more, preferably more than 200 DEG C, more It is more than 250 DEG C, preferably more than 300 DEG C well.The example of suitable flexible base board has poly- (ethylene glycol terephthalate) (PET) and polyethylene glycol (2,6- naphthalene) (PEN).

Anode may include a conductive metal or metal oxide or conducting polymer.Anode can be easily injected into hole Into hole injection layer (HIL) or hole transmission layer (HTL) or luminescent layer.In one embodiment, the work function of anode and The HOMO energy level or valence of illuminator in luminescent layer or the p-type semiconductor material as HIL or HTL or electronic barrier layer (EBL) Absolute value of the difference with energy level is less than 0.5eV, is preferably less than 0.3eV, preferably less than 0.2eV.The example packet of anode material It includes but is not limited to: Al, Cu, Au, Ag, Mg, Fe, Co, Ni, Mn, Pd, Pt, ITO, aluminium-doped zinc oxide (AZO) etc..Other are suitable Anode material be it is known, those of ordinary skill in the art are readily able to select use.Any conjunction can be used in anode material Suitable technology deposition, such as a suitable physical vaporous deposition, including rf magnetron sputtering, vacuum thermal evaporation, electron beam (e- Beam) etc..In certain embodiments, anode is patterning.Patterned ITO electrically-conductive backing plate is commercially available, And it can be used to prepare device according to the present invention.

Cathode may include a conductive metal or metal oxide.Cathode can be easily injected into electronics to EIL or ETL or straight It is connected in luminescent layer.In one embodiment, illuminator or as electron injecting layer in the work function and luminescent layer of cathode (EIL) or the lumo energy of the n-type semiconductor of electron transfer layer (ETL) or hole blocking layer (HBL) or conduction level Absolute value of the difference is less than 0.5eV, is preferably less than 0.3eV, preferably less than 0.2eV.In principle, all yin that can be used as OLED The material of pole all may be as the cathode material of device of the present invention.The example of cathode material includes but is not limited to: Al, Au, Ag, Ca, Ba, Mg, LiF/Al, MgAg alloy, BaF2/Al, Cu, Fe, Co, Ni, Mn, Pd, Pt, ITO etc..Cathode material can be used Any suitable technology deposition, such as a suitable physical vaporous deposition, including rf magnetron sputtering, vacuum thermal evaporation, electronics Beam (e-beam) etc..

OLED can also include other function layer, such as hole injection layer (HIL), hole transmission layer (HTL), electronic barrier layer (EBL), electron injecting layer (EIL), electron transfer layer (ETL), hole blocking layer (HBL).Suitable in these functional layers Material is described later in detail above and in WO2010135519A1, US20090134784A1 and WO2011110277A1, special Full content in this 3 patent documents is incorporated herein by reference by this.

In a preferred embodiment, in luminescent device according to the invention, luminescent layer is by according to the present invention Composition be prepared.

Luminescent device according to the invention, emission wavelength, between 1000nm, preferably arrive 900nm 350 300 Between, preferably 400 between 800nm.

The invention further relates to the application of organic electronic device according to the invention in electronic equipment of various, including, but not It is limited to, shows equipment, lighting apparatus, light source, sensor etc..

The invention further relates to the electronic equipment for including organic electronic device according to the invention, include, but are not limited to show Show equipment, lighting apparatus, light source, sensor etc..

Below in conjunction with preferred embodiment, the present invention is described, but the present invention is not limited to the following examples, It is answered it should be appreciated that appended claims summarise the scope of the present invention those skilled in the art under the guidance of present inventive concept , it is realized that certain change that various embodiments of the present invention are carried out, all by by the spirit of claims of the present invention and Range is covered.

Specific embodiment

Embodiment 1: the synthesis of compound 1

The synthesis of intermediate M2: by 50g2- naphthalene boronic acids, the bromo- 1- iodobenzene of 94g 2- nitro -4-, 10g Pd (PPh₃)₄It is dissolved in 300mLTHF and 50mL H₂The in the mixed solvent of O is reacted for 24 hours for 80 DEG C in a nitrogen atmosphere.It is spin-dried for solvent, methylene chloride extracts, Liquid separation is washed, column chromatographs to obtain intermediate M2.MS (ASAP): 328.17

The synthesis of intermediate M3: 40g intermediate M2 is dissolved in 400mL triethyl phosphite, and 150 DEG C of reactions are for 24 hours.Decompression Solvent is distilled off, column chromatographs to obtain intermediate M3.MS (ASAP): 296.17.

The synthesis of intermediate M4: by 35g intermediate M3,33g connection boric acid pinacol ester and Pd (dppf) Cl₂It is dissolved in In 300mL1,4- dioxane, the lower 100 DEG C of stirrings of nitrogen atmosphere are for 24 hours.It is spin-dried for solvent, extracts liquid separation, column chromatographs to obtain intermediate M4.ASAP(343.23).

The synthesis of intermediate M5: by the chloro- 4- phenylquinazoline of 30g intermediate M4,23g 2-, 4.5g be dissolved in 300mL toluene, The in the mixed solvent of 50mL water, the lower 100 DEG C of stirrings of nitrogen atmosphere are for 24 hours.Vacuum distillation removes solvent, and column chromatographs to obtain intermediate M5.MS(ASAP):421.50.

The synthesis of material 1-1: by 25g intermediate M5,13.5g iodobenzene, 16g cuprous iodide, 13.5g trans cvclohexvl diamines and 25g potassium phosphate is dissolved in the dry toluene of 300mL, in a nitrogen atmosphere 120 DEG C of stirring 12h.Vacuum distillation removes solvent, water It washes, extracts, column chromatographs to obtain compound 1.MS(ASAP):497.62.

Embodiment 2: the synthesis of compound 2

The synthesis of the synthesis reference compound 1 of compound 2, the difference is that changing iodobenzene into intermediate M6.

Embodiment 3: the synthesis of compound 7

The synthesis of compound 7 is referring to embodiment 1, the difference is that changing iodobenzene into intermediate M7.

Embodiment 4: the synthesis of compound 24

The synthesis of the synthesized reference material 1 of compound 24, the difference is that by the chloro- 4- phenyl quinazoline of 2- in compound 1 Oxazoline changes into intermediate M8.MS (ASAP): 586.72.

Embodiment 5: the synthesis of compound 37

The synthesis of intermediate M11: by 50g 1- naphthalene boronic acids, the bromo- 1- iodobenzene of 94g 2- nitro -4-, 10g Pd (PPh₃)₄It is molten In 300mL THF and 50mL H₂The in the mixed solvent of O is reacted for 24 hours for 80 DEG C in a nitrogen atmosphere.Revolving removes solvent, dichloromethane Alkane extraction, washes liquid separation, and column chromatographs to obtain intermediate M11.MS (ASAP): 328.17

The synthesis of intermediate M12: 40g intermediate M11 is dissolved in 400mL triethyl phosphite, and 150 DEG C of reactions are for 24 hours.Subtract Solvent is distilled off in pressure, and column chromatographs to obtain intermediate M12.MS (ASAP): 296.17.

The synthesis of intermediate M13: by 35g intermediate M12,33g connection boric acid pinacol ester and Pd (dppf) Cl₂It is dissolved in In 300mL1,4- dioxane, the lower 100 DEG C of stirrings of nitrogen atmosphere are for 24 hours.It is spin-dried for solvent, extracts liquid separation, column chromatographs to obtain intermediate M13.ASAP(343.23).

The synthesis of intermediate M14: the chloro- 4- phenylquinazoline of 30g intermediate M13,23g 2-, 4.5g are dissolved in 300mL first The in the mixed solvent of benzene, 50mL water, the lower 100 DEG C of stirrings of nitrogen atmosphere are for 24 hours.Vacuum distillation removes solvent, and column chromatographs to obtain centre Body M14.MS (ASAP): 421.50.

The synthesis of compound 37: by 25g intermediate M14,13.5g iodobenzene, 16g cuprous iodide, 13.5g trans cvclohexvl diamines It is dissolved in the dry toluene of 300mL with 25g potassium phosphate, in a nitrogen atmosphere 120 DEG C of stirring 12h.Vacuum distillation removes solvent, water It washes, extracts, column chromatographs to obtain compound 37.MS(ASAP):497.62.

Embodiment 6: the synthesis of compound 15

The synthesis of the synthesis reference compound 1 of compound 15, the difference is that changing iodobenzene into intermediate M15.MS (ASAP):712.86

Embodiment 7: the synthesis of compound 47

The synthesis of the synthesis reference compound 37 of compound 47, the difference is that changing iodobenzene into intermediate M16.MS (ASAP):712.86

Embodiment 8: the synthesis of compound 65

The synthesis of the synthesis reference intermediate M14 of intermediate M18, the difference is that the chloro- 4- phenylquinazoline of 2- is replaced It is changed to MS (ASAP): the 588.71 of M17. intermediate M18

The synthesis of the synthesis reference compound 37 of compound 65, the difference is that changing intermediate M14 into intermediate M18。MS(ASAP):664.81

Embodiment 9: the synthesis of compound 66

The synthesis of the synthesis reference compound 37 of compound 66, the difference is that changing iodobenzene into intermediate M19.MS (ASAP):647.78

Embodiment 11: the synthesis of compound 39

The synthesis of the synthesis reference compound 37 of compound 39, the difference is that changing iodobenzene into intermediate M20.MS (ASAP):547.66

Embodiment 12: the energy level of compound

The energy level of organic compound material can be calculated by quantum, for example (TD-DFT calculation is managed using TD-DFT By) by Gaussian09W (Gaussian Inc.), specific analogy method can be found in WO2011141110.It is passed through first with half Proved recipe method " Ground State/Semi-empirical/Default Spin/AM1 " (Charge 0/Spin Singlet) is come Optimize molecular geometry, then the energy-structure of organic molecule calculates " TD- by TD-DFT (time-depentent DFT) method SCF/DFT/Default Spin/B3PW91 " and base group " 6-31G (d) " (Charge 0/Spin Singlet).HOMO and Lumo energy is calculated according to following calibration equation, S₁, T₁With c resonance coefficient f (S₁) directly use.

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

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

Wherein HOMO (G) and LUMO (G) is the direct calculated result of Gaussian 09W, unit Hartree.As a result such as Shown in table 1:

Table 1: the energy level of compound

Wherein, meet the value of all compound L UMO of general formula (1) close to -2.8eV, triplet T1 is equal More than -2.40eV, illustrate that the compound for meeting general formula (1) shown in embodiment is suitable feux rouges material of main part.All symbols The compound for closing general formula (1) also all has biggish △ HOMO and △ LUMO (△ LUMO > 0.2eV).Wherein, compound 1, chemical combination Object 37, compound 47 can be blended with F-1, F-2 respectively is used as hybrid agent.Meet in table 1 compound of general formula (1) can with it is red Light phosphorescent emitter or TADF illuminator R-1, which are blended, is used as emitting layer material.

The preparation and characterization of embodiment 13:OLED device

Device architecture is ITO/NPD (60nm)/compound 1 or 2 or 37:(piq)₂Ir (acac) (10%) (45nm)/ TPBi(35nm)/Liq(1nm)/Al(150nm).Wherein (piq)₂Ir (acac) is used as luminescent material, and NPD is as hole transport Material, TPBi is as electron transport material, and Liq is as electron injection material.Specific preparation process is as follows:

A, the cleaning of electro-conductive glass substrate: for the first time in use, can be cleaned with multi-solvents, such as chloroform, ketone, isopropyl Alcohol is cleaned, and UV ozone plasma treatment is then carried out；

B, HTL (60nm), EML (45nm), ETL (35m): in high vacuum (1 × 10^-6Millibar, mbar) in hot evaporation form；

C, cathode: LiF/Al (1nm/150nm) is in high vacuum (1 × 10^-6Millibar) in hot evaporation form；

D, encapsulate: device is encapsulated in nitrogen glove box with ultraviolet hardening resin.

Table 2:OLED device performance compares

Current Voltage (J-V) characteristic of each OLED device is characterized by characterization equipment, while recording important parameter such as Efficiency, service life and external quantum efficiency.Table 1 is to compare in the OLED device service life, service life LT95 therein be at constant current, it is bright Degree drops to time when the 95% of original intensity@1000nits.Here LT95 compares device OLED9 and calculates, i.e., With the service life of OLED4 for 1.Through detecting, OLED1 (corresponding compound 1), OLED2 (corresponding compound 2), OLED3 (corresponding chemical combination Object 37), OLED4 (corresponding compound 15), OLED5 (corresponding compound 47), OLED6 (corresponding compound 65), OLED7 it is (corresponding Compound 66), service life of OLED8 (corresponding compound 39) be all 3 times of comparative device OLED9 (respective material CBP) or more, and Comparative device OLED10 (corresponding control compounds F-1, reference literature CN103249800) is apparently higher than as it can be seen that using the present invention Organic mixture preparation OLED device, the service life is improved significantly.

Embodiment 14: the OLED device characterization based on the mixture containing general formula (1) and general formula (2) described compound

Table 3:OLED device performance compares

OLED device	Material of main part	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
			Comparative device OLED15	CBP:F-2	1
Comparative device OLED16	F-1:F-2	1.8

The preparation of device OLED11~OLED16 is referring to embodiment 13, the difference is that material of main part is replaced with table 3 Shown in mixture, wherein the mass ratio of two kinds of components of mixture be 1:1.F-2, F-3 are material described in structure of the invention formula (2) Material, specific synthesized reference document CN201680059397.Current Voltage (J-V) characteristic of each OLED device by characterization equipment come Characterization, while recording important parameter such as efficiency, service life and external quantum efficiency.Table 3 is to compare in the OLED device service life, therein Service life LT95 is that at constant current, brightness drops to time when the 95% of original intensity@1000nits.Here LT95 is phase Comparative device OLED15 (corresponding mixture C BP:F-2) and calculate, i.e., with the service life of OLED15 for 1.Through detecting, OLED11 (corresponding mixture 1:F-2), OLED12 (corresponding mixture 37:F-2), OLED13 (corresponding mixture 47:F-2), OLED14 are (right Answer mixture 37:F-3) service life be all 3 times or more of comparative device OLED15 (corresponding mixture C BP:F-2), and it is obvious high In comparative device OLED16 (corresponding control mixture F-1:F-2), it is seen then that the OLED prepared using organic mixture of the invention Device, service life are improved significantly.

... embodiment 15: the OLED device based on general formula (1) compound and TADF illuminator mixture characterizes

Table 4:OLED device performance compares

OLED device	Material of main part	LT95@1000nits
			OLED17	1	2.9
OLED18	37	3.6
			OLED19	66	4.1
OLED20	39	4.3
			Comparative device OLED21	CBP	1
Comparative device OLED22	F-1	1.3

The preparation of device OLED17~OLED22 is referring to embodiment 13, the difference is that material of main part is replaced with table 4 Compound represented, and by (piq)₂Ir (acac) replace with TADF illuminator R-1 (R-1 bibliography Adv.Mater.2016, 181-187).The luminescent layer of device OLED17~OLED22 is the mixture of host compound and TADF illuminator shown in table 4.Respectively Current Voltage (J-V) characteristic of OLED device is characterized by characterization equipment, while recording important parameter such as efficiency, the service life and External quantum efficiency.Table 3 is to compare in the OLED device service life, and service life LT95 therein is that at constant current, brightness drops to just Beginning brightness@1000nits 95% when time.Here LT95 be compare device OLED21 (corresponding mixture C BP:R-1) and It calculates, i.e., with the service life of OLED21 for 1.Through detecting, OLED17 (corresponding mixture 1:R-1), OLED18 (corresponding mixture 37:R-1), OLED18 (corresponding mixture 66:R-1), OLED19 (corresponding mixture 39:R-1) service life be all comparative device The 2 times or more of OLED21 (corresponding mixture C BP:R-1), and it is apparently higher than comparative device OLED22 (corresponding control mixture F- 1:R-1), it is seen then that the OLED device prepared using organic mixture of the invention, service life are improved significantly.

Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited In contradiction, all should be considered as described in this specification.

The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.

Claims

1. a kind of organic compound of carbazoles containing naphthalene, which is characterized in that have such as structural formula (1-1) or structural formula (1-2) institute The structure shown:

Wherein:

Ar₁、Ar₂Be each independently selected from substitution or the unsubstituted aryl for having 5 to 30 annular atoms perhaps heteroaryl or Selected from substitution or the unsubstituted non-aromatic ring group for having 5 to 30 annular atoms；

R₁、R₂It is each independently selected from H, D, the straight chained alkyl with 1 to 20 C atom, the alcoxyl with 1 to 20 C atom Base, the thio alkoxy with 1 to 20 C atom, the branch with 3 to 20 C atoms or cricoid alkyl have 3 to 20 The branch or cricoid alkoxy of a C atom, branch or cricoid thio alkoxy, monosilane with 3 to 20 C atoms Base, the ketone group with 1 to 20 C atom, the alkoxy carbonyl with 2 to 20 C atoms, the fragrant oxygen with 7 to 20 C atoms Base carbonyl, cyano, carbamoyl, halogen formoxyl, formoxyl, isocyano group, isocyanate group, thiocyanate groups, isothiocyanic acid Ester group, hydroxyl, nitro, CF₃, Cl, Br, F, the substituted or unsubstituted aromatic group with 5 to 30 annular atoms or heteroaryl it is fragrant The combination of group, aryloxy group or heteroaryloxy group or these systems with 5 to 30 annular atoms；

A is 1,2,3 or 4；

B is 1,2,3,4,5 or 6；

When there are multiple R₁When, multiple R₁It is same or different to each other；When there are multiple R₂When, multiple R₂It is same or different to each other；

2. the organic compound of carbazoles containing naphthalene according to claim 1, which is characterized in that the Ar₁、Ar₂For at least A kind of group of such as flowering structure:

Wherein:

When X has multiple in same group, each X is each independently selected from N or CR₅；

When Y has multiple in same group, each Y is each independently selected from CR₆R₇, SiR₆R₇, NR₆Or, C (=O), S,

Or O；

R₅、R₆、R₇The same R of meaning₁。

3. the organic compound of carbazoles containing naphthalene according to claim 2, which is characterized in that the Ar₁、Ar₂Each independently Selected from following group:

Wherein, A O, S, N-Ph or CR₈R₉；R₈、R₉It is each independently C1-C6 alkyl.

4. the organic compound of carbazoles containing naphthalene according to claim 2, which is characterized in that the Ar₁、Ar₂Each independently Selected from following group:

5. the organic compound of carbazoles containing naphthalene according to claim 1-4, which is characterized in that the organic compound Δ HOMO >=the 0.3eV and/or Δ LUMO >=0.2eV of object；Wherein Δ HOMO=((HOMO- (HOMO-1)), Δ LUMO= ((LUMO+1)-LUMO)。

6. wanting the described in any item organic compounds of carbazoles containing naphthalene of 1-4 according to right, which is characterized in that selected from following knot The compound of structure:

7. a kind of high polymer of carbazoles containing naphthalene, which is characterized in that the repetitive unit of the high polymer of carbazoles containing naphthalene includes right It is required that the structure of the described in any item organic compounds of carbazoles containing naphthalene of 1-6.

8. a kind of mixture of carbazoles containing naphthalene, which is characterized in that have including carbazoles containing naphthalene described in any one of claims 1-6 Machine compound or carbazoles containing naphthalene as claimed in claim 7 high polymer, and at least one organic functional material；The organic functions Material is hole-injecting material, hole mobile material, electron transport material, electron injection material, electron-blocking materials, hole resistance Obstructing material, illuminator or material of main part.

9. the mixture of carbazoles containing naphthalene according to claim 8, it is characterised in that: organic functional material is selected from illuminator material Material, luminiferous material are selected from: singlet emitters, triplet emitters and TADF material.

10. according to the described in any item mixtures of carbazoles containing naphthalene of claim 8-9, which is characterized in that further include with structure Second material of main part of structure shown in formula (2):

Wherein, Ar₃,Ar₄It is each independently selected from substitution or the unsubstituted aryl or heteroaryl for there are 5 to 30 annular atoms, or Person replaces or the unsubstituted non-aromatic ring group for having 5 to 30 annular atoms.

11. a kind of composition of carbazoles containing naphthalene, which is characterized in that contain including at least one is described in any one of claims 1-6 Naphthalene carbazoles organic compound or carbazoles containing naphthalene as claimed in claim 7 high polymer, and at least one organic solvent.

12. a kind of organic electronic device, which is characterized in that include at least a kind of click containing naphthalene described in any one of claims 1-6 Azole organic compound, carbazoles containing naphthalene as claimed in claim 7 high polymer or claim 8-10 are described in any item containing naphthalene Carbazoles mixture.

13. organic electronic device according to claim 11, it is characterised in that: include a luminescent layer, wherein including one kind The organic compound of carbazoles containing naphthalene described in any one of claims 1-6, carbazoles containing naphthalene as claimed in claim 7 high polymer or The described in any item mixtures of carbazoles containing naphthalene of claim 8-10.