CN104277063B - A kind of compound based on borazine and the application in organic electronic device - Google Patents

A kind of compound based on borazine and the application in organic electronic device Download PDF

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CN104277063B
CN104277063B CN201410288880.7A CN201410288880A CN104277063B CN 104277063 B CN104277063 B CN 104277063B CN 201410288880 A CN201410288880 A CN 201410288880A CN 104277063 B CN104277063 B CN 104277063B
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潘才法
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Zhejiang Brilliant Optoelectronic Technology Co Ltd
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Abstract

The present invention relates to a kind of novel compounds based on borazine, and including at least has an electron-donating group and an electron-withdrawing group.Compound according to the present invention has big energy gap, and is easy to have lesser Δ (S1-T1), to be easily achieved thermal excitation delayed fluorescence (TADF).The invention further relates to a compositions, include at least one compound according to the invention and at least one organic solvent.It include one or more layers organic functional thin film the present invention further provides a kind of organic electronic device, especially organic luminescent device, wherein at least having thin film includes at least one compound according to the invention.

Description

A kind of compound based on borazine and the application in organic electronic device
Technical field:
The present invention relates to a kind of novel compound based on borazine, including at least having an electron-donating group and an electrophilic Base, and its application in organic electronic device, especially organic luminescent device, and the producer of corresponding organic electronic device Method and its application in illumination and display technology and other occasions.
Background technique:
Organic luminescent device, especially Organic Light Emitting Diode (OLED) are (referring to TANG etc. Appl.Phys.Lett.1987,51, p913), since it is from main light emission, high brightness, it is abundant by chemical synthesis to color Adjustability, flexibility etc. become next-generation display most promising at present and lighting engineering.Especially they may pass through printing Method, such as inkjet printing (InkJet Printing), the technologies such as silk-screen printing (Screen Printing) form a film from solution, So as to substantially reduce manufacturing cost, therefore to large screen display and luminaire with regard to particularly attractive.
OLED performance based on small molecule has significant progress, has reached the commercialized stage.But the property of entirety OLED Can, especially efficiency, the service life still needs to improve.To common organic compound, according to Quantum Spin Statistics, Carrier recombination The ratio for generating singlet and triplet excitons is estimated in 1:3.Due to only having singlet exciton to contribute to shining, so highest Internal quantum is 25%.Current efficient OLED is generally realized by phosphorescent light-emitting materials.Phosphorescent light-emitting materials one As be metallo-organic complex, but it synthesizes complicated, and needs Ir, the rare metals such as Pt there is a problem of at high cost.In addition, Stable blue light, especially dark blue phosphorescent light-emitting materials are not yet.Adachi etc. be recently reported (Nature Vol 492, 234, (2012)) organic thermal excitation delayed fluorescence material (thermally activated delayed fluorescence with Lower abbreviation TADF).This is a technical much progress, and provides a road Tiao Xin to solve the high cost of phosphorescent light-emitting materials. But Adachi etc. report TADF material is only limited to light blue, more dark blue or dark blue material still needs to develop.
Summary of the invention
In order to solve the problems, such as in summary, the present invention provides a kind of novel compound based on borazine, until It less include an electron-donating group and an electron-withdrawing group.Compound according to the present invention has big energy gap, and is easy to have smaller Δ (S1-T1) extend to be easily achieved TADF and can be used for organic luminescent device, especially blue-light device material choosing ?.The present invention relates to a compositions, include at least one compound according to the invention and at least one organic solvent.This hair Bright third purpose is to provide a kind of organic electronic device, especially organic luminescent device, includes that one or more layers is organic Function film, wherein at least having thin film includes at least one compound according to the invention.
The detailed description of invention
It should be appreciated that the specific implementation of the description and display done below is example of the invention, be not meant to In addition any mode limits the scope of the invention.In fact, for purposes of brevity, conventional electricity may be not described in herein Other functions of sub- device, manufacturing method, semiconductor devices and relevant organic material and system.
The present invention provides a kind of novel compound based on borazine, has following general formula 0
Wherein, 1) A is electron-withdrawing group, and core B is the group that one includes borazine, and m, n are the integer of 1-6, feature It is Δ (S1-T1)≤0.30eV of the compound；2) D be electron-donating group, selected from include in following general formula D1-D30 appoint The group of one skeleton:
In a preferred embodiment, it includes group such as flowering structure that core B, which is selected from, and wherein at least one H is inhaled Electronics base A replaces, at least one H is powered subbase D substitution.
In the present invention, Small molecule organic materials refer to that molecular weight is at most the material of 5000g/mol, and molecular weight is higher than The material of 5000g/mol is referred to as high polymer.
In the present invention, organic functional material refers to the organic material with an electronics or optical property, and hole is (also referred to as electric Hole) injection or transmission material (HIM/HTM), hole barrier materials (HBM), electron injection or transmission material (EIM/ETM), electronics Barrier material (EBM), organic host materials (Host), singlet emitters (fluorescent illuminant), triplet emitters (phosphorescence hair Body of light), especially luminescent organometallic complex compound and dyestuff.In the present invention, Host, material of main part, basis material and matrix Material has the same meaning, they can be interchanged.The structural formula of organic functional material, especially its core structure are known as phase The organic functions structural unit answered.Suitable organic functional material and functional architecture unit is being discussed in detail herein below.
In a preferred embodiment, compound according to the invention has following formula 1
Wherein: R1-R6Hydrogen atom, phenyl ring, electron-donating group, electron-withdrawing group or other substituent groups are respectively and independently selected from, but at least There is one selected from electron-donating group, at least one is selected from electron-withdrawing group.
In a preferential embodiment, R in general formula 11-R6In at least there are two being electron-withdrawing group.
In another preferential embodiment, R in general formula 11-R6In at least there are two being electron-donating group.
In a very preferential embodiment, R in general formula 11-R6In at least there are two being electron-withdrawing group, and at least two A is electron-withdrawing group.
In a very preferential embodiment, compound expressed by general formula 1 does not include any metallic element.
Electron-donating group described in general formula 1 can be selected from the group with any skeleton in following formula 2-4:
Wherein: Z1=H, O, S or Si, A1And A2Aromatic rings, miscellaneous aromatic rings, cycloaliphatic ring or non-aromatic can independently be formed Race's heterocycle；In general formula 3, R20It indicates H, aryl, or forms A4Atom group, A necessary to shown ring3And A4It can also be independently Form miscellaneous aromatic rings or non-miscellaneous aromatic rings；In general formula 4, Z2,Z3,Z4,Z5Independently indicate O or S.
In a preferential embodiment, electron-withdrawing group described in general formula 1 can be selected from F, cyano or have following logical The group of any skeleton in formula:
Wherein n is an integer from 1 to 3；X1-X8It selects in CH or N, wherein at least one is N.
In a preferential embodiment, electron-withdrawing group described in general formula 1 is selected from cyano or includes following group:
The triplet T1 of organic material can be measured by low temperature time resolved spectroscopy, or be calculated by quantum simulation (such as pass through
Time-dependent DFT) it obtains, such as have by business software Gaussian 03W (Gaussian Inc.) The analogy method of body can be found in WO2011141110.The singlet energy level S1 of organic material can pass through absorption spectrum, or transmitting light Spectrum can also be calculated (such as Time-dependent DFT) by quantum simulation and obtained to determine.It should be noted that the value of T1 and S1 takes Certainly in measurement or calculation method used.Significant comparison should be based on same method.In description of the invention, T1 and S1 Value be the simulation based on Time-dependent DFT.But other measurements or the application of calculation method are not influenced.
In an especially preferential embodiment, compound according to the invention, Δ (S1-T1)≤0.30eV, compared with Hao Shi≤0.25eV, the Hao Shi≤0.10eV of the Hao Shi≤0.20eV of Geng,.
The present invention also relates to a mixtures, wherein including at least one compound according to the invention, and at least one Organic functional material.Organic functional material can be selected from hole-injecting material (HIM) hole mobile material (HTM) or electricity Sub- barrier material (EBM), electron injection material (EIM) electron transport material (ETM) or hole barrier materials (HBM), Material of main part (Host), fluorescent illuminant or phosphorescent emitter or their various combinations.Suitable organic functional material will It is describing herein below.
In a preferential embodiment, the mixture includes at least one compound according to the invention, And at least one organic host material, wherein the T1 of organic host material is greater than the T1 of compound according to the invention.
In a more preferential embodiment, the mixture includes at least one chemical combination according to the invention Object and at least one organic host material, wherein the T1 of organic host material is greater than the S1 of compound according to the invention.
In certain embodiments, the mixture also includes high polymer material.All includes as described herein small The structure of molecular material is all suitable material as the high polymer material of repetitive unit.In a preferential embodiment, Composition in the present invention includes conjugated highpolymer, and suitable conjugated highpolymer has polyfluorene (polyfluorene), poly- spiral shell-connection Fluorenes (poly (spiro-bifluorene)), poly- indenofluorene (polyindenofluorene), poly- (p-phenylene-Asia ethylene Base) (poly (p-phenylen-vinylene)), poly- (to phenylene) (poly (para-phenylene)), extremely derivative.
The invention further relates to a compositions, wherein including at least one compound according to the invention, at least one has Solvent.The example of organic solvent, including but not limited to, methanol, ethyl alcohol, 2-methyl cellosolve, methylene chloride, three chloromethanes Alkane, chlorobenzene, o-dichlorohenzene, tetrahydrofuran, methyl phenyl ethers anisole, morpholine, toluene, ortho-xylene, meta-xylene, paraxylene, Isosorbide-5-Nitrae dioxy Azacyclohexane, acetone, methyl ethyl ketone, 1,2 dichloroethanes, 3- phenoxytoluene, 1,1,1- trichloroethanes, 1,1,2,2- tetrachloro Ethane, ethyl acetate, butyl acetate, dimethylformamide, dimethyl acetamide, dimethyl sulfoxide, naphthane, naphthalane, indenes and/ Or their mixture.
In a preferential embodiment, composition according to the invention is a solution.
In another embodiment, composition according to the invention is a suspension.
Composition of the invention can include 0.01 to 20wt%, preferably 0.1 to 15wt%, more preferable 0.2 to 10wt%, Most preferably 0.25 to 5wt% organic functional material.The percent data is related to 100% solvent or solvent mixture.
Purposes the invention further relates to the composition as coating or printing ink when preparing organic electronic device, it is special Not preferential is the preparation method by printing or being coated with.
Suitable printing or coating technique includes but is not limited to inkjet printing, typographic printing, silk-screen printing, dip-coating, rotation Turn to be coated with, blade coating, roller printing, torsion roller printing, lithographic printing, flexographic printing, rotary printing, spraying is brushed or moved Print, slit-type squash type coating etc..It is preferred that intaglio printing, silk-screen printing and ink jet printing.Intaglio printing, ink jet printing will It applies in an embodiment of the present invention.Solution or suspension can also comprise one or more components such as surface-active chemical combination Object, lubricant, wetting agent, dispersing agent, hydrophobing agent, bonding agent etc., for adjusting viscosity, filming performance improves adhesion etc..Have Close printing technique, and its to the related request in relation to solution, such as solvent and concentration, viscosity etc., details refer to Helmut Kipphan chief editor " print media handbook: technology and production method " (Handbook of Print Media: Technologies and Production Methods),ISBN 3-540-67326-1。
It include one or more layers organic functional thin film, wherein at least the invention further relates to an organic electronic device Having thin film includes compound according to the invention.
Suitable organic electronic device includes but is not limited to Organic Light Emitting Diode, organic light emission battery, organic photovoltaic electricity Pond, organic field-effect tube, organic light-emitting field effect pipe, organic sensor and organic phasmon emitting diode (Organic Plasmon Emitting Diode).Preferred organic electronic device has Organic Light Emitting Diode, organic light emission battery.
In above-described luminescent device, including a substrate, an anode, at least a luminescent layer, a cathode.Substrate can be It is opaque or transparent.One transparent substrate can be used to manufacture a transparent light emitting component.It see, for example, The Nature such as Bulovic 1996,380, p29 and Gu etc., Appl.Phys.Lett.1996,68, p2606.Substrate can be just It is property or elastic.Substrate can be plastics, metal, semiconductor wafer or glass.Preferably substrate has a smooth surface. Substrate free of surface defects is especially desirable selection.In a preferential embodiment, substrate it is optional in thin polymer film or Plastics, glass transition temperature Tg is 150 DEG C or more, preferably more than 200 DEG C, more preferably more than 250 DEG C, preferably more than 300 ℃.The example of suitable substrate 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 HIL or HTL or luminescent layer.In one embodiment, inorganic semiconductor illuminator in the work function and luminescent layer of anode Or the HOMO energy level of the p-type semiconductor material as HIL or HTL or EBL or the absolute value of the difference of valence-band level are less than 0.5eV, Preferably it is less than 0.3eV, preferably less than 0.2eV.The example of anode material 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 suitable anode materials be it is known, this field is common Technical staff is readily able to select use.Any suitable technology deposition, such as a suitable physics gas can be used in anode material Phase sedimentation, 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, inorganic semiconductor illuminator or as EIL in the work function and luminescent layer of cathode Or the lumo energy of the n-type semiconductor of ETL or HBL or the absolute value of the difference of conduction level are less than 0.5eV, are preferably less than 0.3eV, preferably less than 0.2eV.In principle, the material of all cathodes that can be used as OLED all may be as device of the present invention Cathode material.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..Any suitable technology deposition, such as a suitable object can be used in cathode material Physical vapor deposition method, including rf magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam) etc..
In a preferential embodiment, in luminescent device according to the invention, luminescent layer is by the printing present invention Composition be prepared.
The invention further relates to the application of luminescent device according to the invention in electronic equipment of various, include, but are not limited to Show equipment, lighting apparatus, light source, sensor etc..
The invention further relates to the electronic equipments for including luminescent device according to the invention, include, but are not limited to display and set It is standby, lighting apparatus, light source, sensor etc..
Some more detailed descriptions (but not limited to this) are made to organic functional material below.In principle, all to be used for The organic functional material of OLEDs, including hole (also referred to as electric hole) injection or transmission material (HIM/HTM), hole barrier materials (HBM), electron injection or transmission material (EIM/ETM), electron-blocking materials (EBM), organic host materials (Host), singlet state Illuminator (fluorescent illuminant), weight state illuminator (phosphorescent emitter), especially luminescent organometallic complex compound, dyestuff (Dye), It can be used in luminescent device of the invention.Such as in WO2010135519A1, US20090134784A1 and WO Various organic functional materials are described later in detail in 2011110277A1, hereby simultaneously by the full content in this 3 patent document Enter herein as reference.
1.HIM/HTM
Suitable organic HTM material is optional include following structural unit compound: phthalocyanine (phthlocyanine), Porphyrin (porphyrine), amine (amine), aromatic amine, biphenyl class triaryl amine (triarylamine), thiophene (thiophene), Bithiophene (fused thiophene) such as dithienothiophene (dithienothiophene) and bithiophene (dibenzothiphene), pyrroles (pyrrole), aniline (aniline), carbazole (carbazole), indolocarbazole (indolocarbazole), and their derivative.The suitable HTM of another position also includes containing fluorohydrocarbon (fluorohydrocarbon) polymer；Polymer containing conductiving doping；Conducting polymer, such as PEDOT/PSS；From group Fill monomer, such as compound containing phosphonic acids and sliane derivative；Metal oxide, such as MoOx；Metal complex and Cross-linked Close object etc..
The example that can be used as the cyclophane perfume (or spice) amine derivative compounds of HIM or HTM includes but is not limited to following general structure:
Each Ar1To Ar9It can be independently selected from aromatic hydrocarbon ring compound, such as benzene, biphenyl, triphenyl, benzo, naphthalene, anthracene, Phenalene, luxuriant and rich with fragrance, fluorenes, pyrene are bent, Azulene；Heteroaromatic compound, such as dibenzothiophenes, dibenzofurans, furans, thiophene, Benzofuran, benzothiophene, carbazole, pyrazoles, imidazoles, triazole, isoxazole, thiazole, oxadiazoles, oxatriazole, two dislike Azoles, thiadiazoles, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazines, oxathiazine, oxadiazine, indoles, benzimidazole, Indazole, indoxazine, benzoxazoles, benzisoxazole, benzothiazole, quinoline, isoquinolin, cinnoline, quinoline azoles Quinoline, quinoxaline, naphthalene, phthalein, pteridine, xanthene, acridine, azophenlyene, phenthazine, phenoxazine, dibenzoselenophene, Benzoselenophene, benzofuropyridine, indolocarbazole, pyridylindole, Pyrrolodipyridine, furodipyridine, benzothienopyridine, thienodipyridine, Benzoselenophenopyridine and selenophenodipyridine；It include the group of 2 to 10 ring structures, they It can be the aromatic hydrocarbon ring group or aromatic heterocycle group of identical or different type, and directly with one another or by below at least one Group link together, such as oxygen atom, nitrogen-atoms, sulphur atom, silicon atom, phosphorus atoms, boron atom, chain structural unit and fat Cyclic group.Wherein, each Ar can be further substituted, and substituent group is chosen as hydrogen, alkyl, alkoxy, amino, alkene, alkynes, aralkyl Base, miscellaneous alkyl, aryl and heteroaryl.
In one aspect, Ar1To Ar9It can be independently selected from comprising the group such as the following group:
N is 1 to 20 integer；X1To X8It is CH or N；Ar1It is aryl or heteroaryl.
The other example of cyclophane perfume (or spice) amine derivative compounds can be found in US3567450, US4720432, US5061569, US3615404, and US5061569.
The example that can be used as the metal complex of HTM or HIM includes but is not limited to following general structure:
M is a metal, there is the atomic weight greater than 40；
(Y1-Y2) it is one liang of tooth ligand, Y1And Y2Independently selected from C, N, O, P, and S；L is an assistant ligand；M is one Integer, value from 1 to this metal maximum coordination number；M+n is the maximum coordination number of this metal.
In one embodiment, (Y1-Y2) it is a 2- phenylpyridine derivative
In another embodiment, (Y1-Y2) it is a carbenes
In another embodiment, M choosing is in Ir, Pt, Os, and Zn.
On the other hand, the HOMO of metal complex is greater than -5.5eV (relative to vacuum level)
The example that suitably can be used as HIM/HTM compound is listed in following table:
2.EIM/ETM
In principle, suitable N-shaped organic semiconducting materials are optional in all EIM/ETM for OLEDs.EIM/ETM The example of material is not particularly limited, and any metal complex or organic compound may all be used as ETM, as long as it Can transmit electronics.Preferential organic ETM material can be selected from three (8-hydroxyquinoline) aluminium (AlQ3), azophenlyene (Phenazine), Phenanthroline (Phenanthroline), anthracene (Anthracene), luxuriant and rich with fragrance (Phenanthrene), fluorenes (Fluorene), two fluorenes (Bifluorene), two fluorenes of spiral shell (Spiro-bifluorene), to phenylacetylene (Phenylene-vinylene), triazine (triazine), triazole (triazole), imidazoles (imidazole), pyrene (Pyrene), (Perylene), anti-indenofluorene (trans-Indenofluorene), along indeno (cis-Indenonfluorene), dibenzo-indenofluorene (Dibenzol- ), indenofluorene indeno naphthalene (Indenonaphthalene), benzanthracene (benzanthracene) and their derivative Object
On the other hand, the compound that can be used as EIM/ETM is the molecule for containing at least one following group:
R1It is optional in following group: hydrogen, alkyl, alkoxy, amino, alkene, alkynes, aralkyl, miscellaneous alkyl, aryl and heteroaryl Base, the Ar when they are aryl or heteroaryl, in they and above-mentioned HTM1And Ar2Meaning is identical；
Ar1-Ar5With the Ar described in HTM1Meaning is identical；
N is an integer from 0 to 20；
X1-X8It selects in CH or N, wherein at least one is N.
On the other hand, the example that can be used as the metal complex of EIM/ETM includes but is not limited to following general structure:
(O-N) or (N-N) is one liang of tooth ligand, wherein metal and O, N or N, N coordination；L is an assistant ligand；M is one Integer, value from 1 to this metal maximum coordination number.
In another preferential embodiment, organic alkali metal compound can be used as EIM.In the present invention, organic base It is following compound that metallic compound, which is understood that dig, and wherein at least one alkali metal, i.e. lithium, sodium, potassium, rubidium, caesium goes forward side by side One step includes at least one organic ligand.
In suitable organic alkali metal compound, including US 7767317B2, EP 1941562B1 and EP 1144543B1 Described compound.
The organic alkali metal compound preferentially selected is the compound of following chemical formula:
Wherein R1Meaning as described above, camber line represents two or three atoms and bonded, so as to when necessary with metal M 5 yuan or hexatomic ring are formed, wherein atom can also be by one or more R1Replace, M is alkali metal, be selected from lithium, sodium, potassium, rubidium, Caesium.Organic alkali metal compound can have the form of monomer, as described above, or have the form of aggregation, for example, two alkali are golden Belong to ion and two ligands, 4 alkali metal ions and 4 ligands, 6 alkali metal ions and 6 ligands or in other forms.
The organic alkali metal compound especially preferentially selected is the compound of following chemical formula:
Symbol used in it is identical as aforementioned definitions, in addition: M is alkali metal element
O, can be identical or different when occurring every time, be 0,1,2,3 or 4；
P, can be identical or different when occurring every time, be 0,1,2 or 3；
In a preferential embodiment, alkali metal M is selected from lithium, sodium, potassium, more preferably lithium or sodium, preferably lithium.
In a preferential embodiment, in organic alkali metal compound electron injecting layer preferably, electron injecting layer It is made of organic alkali metal compound.
In another preferential embodiment, organic alkali metal compound is doped in other ETM and forms electron-transport Is electron transfer layer preferably in layer or electron injecting layer.
The example of suitable organic alkali metal compound is listed in following table:
3. triplet host material (Triplet Host):
The example of triplet host material is not particularly limited, and any metal complex or organic compound all may It is used as matrix, as long as its triplet energy ratio illuminator, especially triplet emitters or phosphorescent emitter are higher.
The example that can be used as the metal complex of triplet matrix (Host) includes but is not limited to following general structure:
M is a metal；(Y3-Y4) it is one liang of tooth ligand, Y3And Y4Independently selected from C, N, O, P, and S；L is an auxiliary Ligand；M is an integer, value from 1 to this metal maximum coordination number；M+n is the maximum coordination number of this metal.
In a preferential embodiment, the metal complex that can be used as triplet matrix has following form:
It (O-N) is one liang of tooth ligand, wherein metal and O and N Atomic coordinate
In some embodiment, M is optional in Ir and Pt.
Can be used as the organic compound of triplet matrix example be selected from include aromatic hydrocarbon ring base compound, hinder as Benzene, biphenyl, triphenyl, benzo, fluorenes；Test；It include the compound of fragrant heterocyclic radical, such as dibenzothiophenes, dibenzofurans, Dibenzoselenophene, furans, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, Indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazoles, imidazoles, triazole type, oxazole, thiazole are disliked Diazole, oxatriazole, dioxazole, thiadiazoles, pyridine, pyridazine, pyrimidine, pyrazine, triazines, oxazines, Oxathiazines, oxadiazines, indoles, benzimidazole, indazole, indoxazine, bisbenzoxazoles, Benzisoxazole, benzothiazole, quinoline, isoquinolin, cinnoline, quinazoline, quinoxaline, naphthalene, phthalein, pteridine, xanthene, Acridine, azophenlyene, phenthazine, phenoxazines, benzofuropyridine, furodipyridine, Benzothienopyridine, thienodipyridine, benzoselenophenopyridine and selenophenodipyridine；It include the group of 2 to 10 ring structures, they can be the cyclophane of identical or different type Fragrant hydrocarbyl group or aromatic heterocycle group, and link together directly with one another or by least one group below, such as oxygen atom, Nitrogen-atoms, sulphur atom, silicon atom, phosphorus atoms, boron atom, chain structural unit and aliphatic cyclic group.Wherein, each Ar can be into one Step is substituted, and substituent group is chosen as hydrogen, alkyl, alkoxy, amino, alkene, alkynes, aralkyl, miscellaneous alkyl, aryl and heteroaryl.
In a preferential embodiment, triplet host material is optional in the chemical combination comprising at least one following group Object:
R1-R7It can select independently of each other in following group: hydrogen, alkyl, alkoxy, amino, alkene, alkynes, aralkyl, miscellaneous alkane Base, aryl and heteroaryl, the Ar when they are aryl or heteroaryl, in they and above-mentioned HIM/HTM1And Ar2Meaning is identical；n It is an integer from 0 to 20；X1-X8It selects in CH or N；X9It selects in CR1R2Or NR1。
4. singlet state host material (Singlet Host):
The example of singlet state host material is not particularly limited, and any organic compound may all be used as base Matter, as long as its singlet energy is higher than illuminator, especially singlet emitters or fluorescent illuminant.
The example of the organic compound used as singlet state host material can be selected from containing aromatic hydrocarbon ring compound, such as Benzene, biphenyl, triphenyl, benzo, naphthalene, anthracene, phenalene is luxuriant and rich with fragrance, fluorenes, and pyrene is bent, Azulene；Heteroaromatic compound, such as dibenzo Thiophene, dibenzofurans, dibenzoselenophene, furans, thiophene, benzofuran, benzothiophene, Benzoselenophene, carbazole, indolocarbazole, pyridylindole, Pyrrolodipyridine, pyrazoles, miaow Azoles, triazole, isoxazole, thiazole, oxadiazoles, oxatriazole, dioxazole, thiadiazoles, pyridine, pyridazine, pyrimidine, pyrazine, three Piperazine, oxazines, oxathiazine, oxadiazine, indoles, benzimidazole, indazole, indoxazine, benzoxazoles, Benzisoxazole, benzothiazole, quinoline, isoquinolin, cinnoline, quinazoline, quinoxaline, naphthalene, phthalein, pteridine, xanthene, Acridine, azophenlyene, phenthazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, Thienodipyridine, benzoselenophenopyridine and selenophenodipyridine；It include 2 to 10 The group of ring structure, they can be the aromatic hydrocarbon ring group or aromatic heterocycle group of identical or different type, and directly with one another Or linked together by least one group below, such as oxygen atom, nitrogen-atoms, sulphur atom, silicon atom, phosphorus atoms, boron original Son, chain structural unit and aliphatic cyclic group.
In a preferential embodiment, singlet state host material is optional in the chemical combination comprising at least one following group Object:
R1-R7It can select independently of each other in following group: hydrogen, alkyl, alkoxy, amino, alkene, alkynes, aralkyl, miscellaneous alkane Base, aryl and heteroaryl, when they are aryl or heteroaryl, they and above-mentioned Ar1And Ar2Meaning is identical；
N is an integer from 0 to 20；X1-X8It selects in CH or N；X9, X10It selects in CR1R2Or NR1。
5. hole barrier materials (HBM)
Hole blocking layer (HBL) is commonly used to stop the hole from successive functional layers, especially luminescent layer.Comparison one There is no the OLED on barrier layer, the presence of HBL normally results in the raising of luminous efficiency.The hole barrier of hole blocking layer (HBL) Material (HBM) is needed than successive functional layers, and if the lower HOMO. of luminescent layer is in a preferential embodiment, HBM has ratio The bigger excited level of adjacent emissive layers, such as singlet state or triplet, depending on illuminator in another preferential embodiment party In case, HBM has electron-transport function
In one embodiment, contain molecule identical with luminescent layer mesostroma material as HBM.
In another preferential embodiment, HBM is optional in the compound comprising at least one following group:
N is an integer from 0 to 20；L is an assistant ligand；M is an integer from 1 to 3.
6. 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 (styrylamine) and its derivative, and in WO2008/ Indenofluorene disclosed in 006449 and WO2007/140847 (indenofluorene) and its derivative.
In a preferential embodiment, singlet emitters can be selected from unitary styrylamine (monostyrylamines), binary styrylamine (distyrylamines), ternary styrylamine (tristyrylamines), quaternary styrylamine (tetrastyrylamines), styrene phosphine (styrylphosphines), Styrene ether (styryl ethers) and arylamine (arylamines).
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 (diarylamino) is directly linked on anthracene, preferably 9 On position.One fragrant anthradiamine refers to that a compound, wherein two binary arylamine group (diarylamino) are directly linked to 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, Wherein binary arylamine group is preferably linked 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.
Example based on stibene (distyrylbenzene) extremely singlet emitters of 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 (benzoindenofluorene-amine) and benzo indenofluorene-diamines (benzoindenofluorene-diamine), as disclosed in WO 2008/006449, dibenzo indenofluorene-amine (dibenzoindenofluorene-amine) and dibenzo indenofluorene-diamines (dibenzoindenofluorene- Diamine), as disclosed in WO2007/140847.
Other materials that can be used as singlet emitters have polycyclic aromatic hydrocarbon compounds, the derivative of especially following compound Object: anthracene such as 9,10- bis- (2- naphthanthracene) (9,10-di (2-naphthylanthracene)), naphthalene, four benzene, xanthene are luxuriant and rich with fragrance (phenanthrene), pyrene (perylene) such as 2,5,8,11-tetra-t-butylperylene, indeno pyrene (indenoperylene), penylene (phenylenes) such as (4,4 '-(bis (9-ethyl-3-carbazovinylene) -1, 1 '-biphenyl), periflanthene, decacyclene (decacyclene), coronene (coronene), fluorenes, two fluorenes of spiral shell (spirofluorene), aryl pyrene (arylpyrene) (such as US20060222886), arylene ethylene (arylenevinylene) (such as US5121029, US5130603), cyclopentadiene such as tetraphenyl cyclopentadiene (tetraphenylcyclopentadiene), rubrene (rubrene), cumarin (coumarine), rhodamine (rhodamine), quinacridone (quinacridone), pyrans (pyrane) such as 4 (dicyanoethylene) -6- (4- Dimethylaminostyryl-2-methyl) -4H-pyrane (DCM), thiapyran (thiapyran), bis (azinyl) Imine-boron compound (2007/0092753 A1 of US), bis (azinyl) methene compound, carbostyrylization Close object, oxazinone (oxazone), benzoxazoles (benzoxazole), benzothiazole (benzothiazole), benzimidazole (benzimidazole) and diketopyrrolopyrrole.The material of some singlet emitters can be in following patent documents In find: US 20070252517 A1, US 4769292, US 6020078, US 2007/0252517 A1, US 2007/ 0252517 A1.The full content in the above-mentioned patent document listed is incorporated herein by reference hereby.
7. triplet emitters (Triplet Emitter)
Triplet emitters are also referred to as phosphorescent emitter.In a preferential embodiment, triplet emitters be have it is logical The metal complex of formula M (L) n, wherein M is a metallic atom, can be identical or different when L occurs every time, is one organic to match Body, 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 select It is 1,2,3,4,5 or 6.Optionally, these metal complexes are connected on a polymer by one or more positions, best It is 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,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 (phenylpyridine) derivative, 7,8- benzoquinolines (7,8- Benzoquinoline) derivative, 2 (2- thienyl) pyridines (2 (2-thienyl) pyridine) derivative, 2 (1- naphthalene) pyrroles Pyridine (2 (1-naphthyl) pyridine) derivative or 2 phenylchinolines (2phenylquinoline) derivative.It is all these Organic ligand may be all substituted, such as be replaced by fluorine-containing or trifluoromethyl.Assistant ligand can be preferably selected from acetic acid acetone (acetylacetonate) 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 lanthanide series or actinides；
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；It can be identical or different when L occurs every time, be an assistant ligand, be preferable over double-tooth chelate ligand, Preferably monoanionic, bidentate cheland；M is 1,2 or 3, is preferentially 2 or 3, is especially preferentially 3；N is 0,1, or 2, excellent It is first 0 or 1, is especially preferentially 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.,JACS 105,1983,1795,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.The full content in the above-mentioned patent document and document listed is incorporated herein by reference hereby.
8. dyestuff (Dye)
In principle, all to be used for organic photovoltaic battery, including DSSC, organic functions dyestuff, can be used in the present invention Electronic device in.Suitable dyestuff is selected from the multi-pyridine ligand of transition metal, preferably ruthenium, osmium, the metal complex dye of copper Material.In a preferred embodiment, the general structure ML2 (X) 2 of metal complex dyes, wherein L is preferably selected from 2,2'- connection In pyridine -4,4'- dicarboxylic acids, M is transition metal, and excellent dyestuff is selected from Ru, Os, Fe, and V and Cu, X are selected from halide, cyaniding The substituent group of object, rhodanate, acetylacetonate compound, thiocarbamate or water.These premetallized dyes are following Document in be disclosed The Journal of Physical Chemistry C 2009,113,2966-2973, US2009000658,WO2009107100,WO2009098643,US6245988,WO2010055471,JP2010084003, EP1622178,WO9850393,WO9529924,WO9404497,WO9214741,WO9116719.It is listed hereby by above-mentioned Full content in patent document and document is incorporated herein by reference.
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 understood that appended claims summarise the scope of the present invention those skilled in the art under the guidance of present inventive concept Recognize, to certain change that various embodiments of the present invention are carried out, all by by claims of the present invention spirit and Range is covered.
Specific embodiment
1. the synthesis of compound F1-F4
General synthesis path, at room temperature (300K), the anion and fluorination cyano boron azane of carbazole are anti-under nitrogen atmosphere It answers 16 hours.Products therefrom passes through column chromatography on silica gel and is purified, reprecipitation.Surveying luminescence generated by light and electroluminescent light Before spectrum, the further sublimation purification of compound.
2. the energy-structure of compound F1-F4
The energy-structure of compound F1-F4 can be calculated by quantum, for example (TD-DFT calculation is managed using TD-DFT By) by Gaussian03W (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, and S1 and T1 are directly used.
HOMO (eV)=((HOMO (Gaussian) × 27.212) -0.9899)/1.1206
LUMO (eV)=((LUMO (Gaussian) × 27.212) -2.0041)/1.385
Wherein HOMO (Gaussian) and LUMO (Gaussian) is the direct calculated result of Gaussian 03W, and unit is Hartree.As a result as shown in Table 1:
Table one
Compound HOMO[eV] LUMO[eV] S1[eV] T1[eV] Δ(S1-T1)[eV]
F1 -5,98 -3,01 2,97 2,95 0,02
F2 -6,00 -2,95 3,09 3,06 0,03
F3 -6,07 -2,89 3,10 3,06 0,04
H1 -6,51 -2,21 3,70 3,12 0,59
Δ (S1-T1)≤0.10eV of wherein F1, F2, F3.
3. photoluminescence spectra
F1, F2, F3 photoluminescence spectra measure in toluene.Substantially in 416nm, the peak value of F2 substantially exists the peak value of F1 The peak value of 407nm, F3 are substantially in 404nm.
The preparation and measurement of 4.OLEDs
Following material of main part H1 is used as material of main part of the invention.The synthesis of H1 can be found in Appl.Phys.Lett.Vol88,183503 and its bibliography.The T1 of H1 is higher than F1, the S1 of F2, F3.
OLEDs vacuum evaporation forms, and structure is as follows:
ITO (50nm)/NPD (40nm)/H1:Fx (5wt%) (15nm)/TPBi (65nm)/LiF (1nm)/Al (100nm)
(the Keithley 2400source that Current Voltage (I-V) characteristic of OLED is controlled by computer Measurement unit) and (Keithley 2000multimeter) record, simultaneously, brightness is by using calibration Silicon photoelectric diode (Newport 2112) measurement crossed.Electroluminescent spectrum passes through spectrometer (Ocean Optics USB2000 it) measures.OLED1-3 sends out light dark blue under the voltage of 3V or more, their performance is summarised in following table 2 In, wherein EQE (External Quantum Efficiency) indicates external quantum efficiency.The EQE of all OLED1-3 is super 9% is crossed, for dark blue, this very high value.
Table 2
Device Ignition voltage (V) Maximum EQE (%)
OLED1 3.05 11.2%
OLED2 3.10 9.4%
OLED3 2.97 9.1%

Claims (10)

1. a kind of compound according to following general formula 0:
Wherein: 1) A is electron-withdrawing group, and core B is the group that one includes borazine, and m, n are the integer of 1-6, it is characterised in that Δ (S1-T1)≤0.30eV of the compound；2) D is electron-donating group, selected from including any bone in following general formula D1-D30 The group of frame:
2. compound according to claim 1, it includes group such as flowering structure that center B, which is selected from:
Wherein at least one H is replaced by electron-withdrawing group A, at least one H is powered subbase D substitution.
3. compound according to claim 1 has following formula 1:
Wherein: R1-R6It is respectively and independently selected from hydrogen atom, electron-donating group, electron-withdrawing group, but at least one is selected from electron-donating group, until Rare one is selected from electron-withdrawing group.
4. compound according to claim 1, wherein the electron-withdrawing group A is selected from F, cyano or include following general formula The group of any skeleton in A1-A25:
5. compound according to claim 1, Δ (S1-T1)≤0.20eV.
It include a kind of compound according to claim 1 and another organic functional material 6. a kind of mixture, it is organic Functional material is injected selected from hole or transmission material, hole barrier materials, electron injection or transmission material, electron-blocking materials, Organic host materials, singlet emitters, triplet emitters and dyestuff.
7. a kind of composition includes at least one compound according to claim 1 and at least one organic solvent.
8. application of the compound according to claim 1 in organic electronic device, organic electronic device is selected from organic light emission two Pole pipe, organic photovoltaic battery, organic field-effect tube, organic sensor and organic phasmon emitting diode (Organic Plasmon Emitting Diode)。
9. a kind of organic electronic device, including at least there is a kind of compound according to claim 1.
10. organic electronic device according to claim 9 can be selected from Organic Light Emitting Diode, organic photovoltaic battery, organic field effect Ying Guan, organic sensor and organic phasmon emitting diode (Organic Plasmon Emitting Diode).
CN201410288880.7A 2013-07-07 2014-06-25 A kind of compound based on borazine and the application in organic electronic device Active CN104277063B (en)

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