CN104277063A - Borazine-based compound and application thereof in organic electronic device - Google Patents

Borazine-based compound and application thereof in organic electronic device Download PDF

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CN104277063A
CN104277063A CN201410288880.7A CN201410288880A CN104277063A CN 104277063 A CN104277063 A CN 104277063A CN 201410288880 A CN201410288880 A CN 201410288880A CN 104277063 A CN104277063 A CN 104277063A
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潘才法
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Zhejiang Brilliant Optoelectronic Technology Co Ltd
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Abstract

The invention relates to a novel borazine-based compound which at least comprises an electron donating group and an electron withdrawing group. The compound according to the invention has a large energy cap, and easily has relatively small delta (S1-T1), thus thermally activated delayed fluorescence (TADF) is easily realized. The invention further relates to a composition which comprises at least one compound according to the invention and at least one organic solvent. The invention further provides an organic electronic device and particularly relates to an organic light-emitting device which comprises one or more layers of organic functional films, wherein at least one layer of film comprises at least one compound according to the invention.

Description

A kind of based on the compound of borazine and the application in organic electronic devices
Art:
The present invention relates to a kind of novel compound based on borazine, at least include an electron-donating group and an electron withdrawing group, and at organic electronic devices, application particularly in organic luminescent device, and the production method of organic electronic devices and the application in illumination and technique of display and other occasions thereof accordingly.
Background technology:
Organic luminescent device, particularly Organic Light Emitting Diode (OLED) is (see Appl.Phys.Lett.1987 such as TANG, 51, p913), because it is from main light emission, high brightness, abundant by the adjustability of chemosynthesis to color, flexible etc. become current most promising next generation's display and lighting engineering.Particularly they can by the method printed, as spray ink Printing (InkJet Printing), technology film forming from solution such as silk screen printing (Screen Printing), thus greatly can reduce manufacturing cost, therefore just attractive especially to large screen display and luminaire.
Have significant progress based on micromolecular OLED performance, reach the business-like stage.But the performance of overall OLED, particularly efficiency, the life-span still needs to improve.To common organic compound, according to Quantum Spin Statistics, the ratio that Carrier recombination produces singlet and triplet excitons is estimated at 1:3.Owing to only having singlet exciton to have contribution to luminescence, so the highest internal quantum is 25%.Current high efficiency OLED is generally realized by phosphorescent light-emitting materials.Phosphorescent light-emitting materials is generally metallo-organic complex, but its synthesis is complicated, and needs Ir, the rare metals such as Pt, there is the problem that cost is high.In addition, stable blue light, particularly dark blue phosphorescent light-emitting materials does not also have.Adachi etc. are recently reported (Nature Vol492,234, (2012)) organic thermal excitation delayed fluorescence material (thermally activated delayed fluorescence is hereinafter referred to as TADF).This is a technical much progress, and is that the high cost solving phosphorescent light-emitting materials provides a Tiao Xin road.But Adachi etc. report TADF material is only limited to light blue, more dark blue or dark blue material still needs exploitation.
Summary of the invention
In order to solve problem in sum, the invention provides a kind of novel compound based on borazine, it at least includes an electron-donating group and an electron withdrawing group.According to compound of the present invention, there is large energy gap, and be easy to that there is less Δ (S1-T1), thus be easy to realize TADF, extend and can be used for organic luminescent device, particularly the material options of blue-light device.The present invention relates to a composition, include at least one according to compound of the present invention and at least one organic solvent.3rd object of the present invention is to provide a kind of organic electronic devices, particularly organic luminescent device, includes one or more layers organic functional thin film, wherein has at least thin film to include at least one according to compound of the present invention.
The detailed description of invention
Will be appreciated that, the concrete enforcement of description done below and display is example of the present invention, and does not mean that and limit the scope of the invention in addition by any way.In fact, for succinct object, may not describe conventional electronics, manufacture method, semiconducter device in detail at this, and relevant organic materials, and other function of system.
The invention provides a kind of novel compound based on borazine, there is following general formula 0
Wherein D is electron-donating group, and A is electron withdrawing group, and core B is a group including borazine, and m, n are the integer of 1-6.
In a preferred embodiment, core B is selected from the group including following structure, and wherein any two H can be replaced by electron withdrawing group A or electron-donating group D or other groups.
In the present invention, Small molecule organic materials refers to that molecular weight is at most the material of 5000g/mol, and molecular weight is referred to as superpolymer higher than the material of 5000g/mol.
In the present invention, organic functional material refers to the organic materials with an electronics or optical property, hole (also claiming electric hole) is injected or transport material (HIM/HTM), hole barrier materials (HBM), electron injection or transport material (EIM/ETM), electron-blocking materials (EBM), organic host materials (Host), singlet emitters (fluorescent illuminant), triplet emitters (phosphorescent emitter), particularly luminescent organometallic complex compound, and dyestuff.In the present invention, Host, material of main part, body material and substrate material have identical implication, and they can exchange.The structural formula of organic functional material, particularly its core structure are called corresponding organic functions structural unit.The organic functional material be applicable to, and functional architecture unit has detailed description after this paper.
In a preferred embodiment, according to compound of the present invention, there is following general formula 1
Wherein: R 1-R 6independently be selected from hydrogen atom, phenyl ring, electron-donating group, electron withdrawing group or other substituting groups, but have at least one to be selected from electron-donating group, have at least one to be selected from electron withdrawing group.
In a preferential embodiment, R in general formula 1 1-R 6in have at least two to be electron withdrawing group.
In the embodiment that another is preferential, R in general formula 1 1-R 6in have at least two to be electron-donating group.
In a very preferential embodiment, R in general formula 1 1-R 6in have at least two to be electron withdrawing group, and have at least two to be electron withdrawing group.
In a very preferential embodiment, the compound expressed by general formula 1 does not comprise any metallic element.
Electron-donating group described in general formula 1 can be selected from the group with arbitrary skeleton in following general formula 2-4:
Wherein: Z 1=H, O, S or Si, A 1and A 2independently can form aromatic nucleus, assorted aromatic nucleus, cycloaliphatic ring or non-aromatic heterocyclic; In general formula 3, R 20represent H, aryl, or form A 4the shownschematically necessary atom group of ring, A 3and A 4also assorted aromatic nucleus or non-assorted aromatic nucleus can independently be formed; In general formula 4, Z 2, Z 3, Z 4, Z 5independently represent O or S.
In a preferential embodiment, the electron-donating group described in general formula 1 is selected from the group including arbitrary skeleton in following general formula D 1-D30:
Electron withdrawing group described in general formula 1 can be selected from F, cyano group or have the group of arbitrary skeleton in following general formula:
Wherein n be one from 1 to 3 integer; X 1-X 8select in CH or N, wherein have at least one to be N.
In a preferential embodiment, the electron withdrawing group described in general formula 1 is selected from cyano group or includes following group:
The triplet T1 of organic materials measures by low temperature time resolved spectroscopy, or obtained, as passed through business software Gaussian03W (Gaussian Inc.) by quantum simulation calculating (as by Time-dependent DFT). concrete analogy method can see WO2011141110.The singlet energy level S1 of organic materials, by absorption spectrum, or emmission spectrum is determined, also calculates (as Time-dependent DFT) by quantum simulation and obtains.It should be noted that the value of T1 and S1 depends on measurement used or method of calculation.Significant comparison should based on same method.In description of the invention, the value of T1 and S1 is the simulation based on Time-dependent DFT.But do not affect the application of other measurements or method of calculation.
In a preferential especially embodiment, according to compound of the present invention, its Δ (S1-T1)≤0.30eV, better Shi≤0.25eV, more Hao Shi≤0.20eV, the most Hao Shi≤0.10eV.
The present invention also relates to a mixture, wherein include at least one according to compound of the present invention, and the organic functional material of at least one.Organic functional material can be selected from hole-injecting material (HIM) or hole mobile material (HTM) or electron-blocking materials (EBM), electron injection material (EIM) or 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 describe after this paper.
In a preferential embodiment, described mixture includes at least one according to compound of the present invention, and the organic host material of at least one, and wherein the T1 of organic host material is greater than the T1 according to compound of the present invention.
In a more preferential embodiment, described mixture includes at least one according to compound of the present invention, and the organic host material of at least one, and wherein the T1 of organic host material is greater than the S1 according to compound of the present invention.
In certain embodiments, described mixture also includes high polymer material.All structures including small molecule material as herein described are all suitable materials as the high polymer material of repeating unit.In a preferential embodiment, composition in the present invention includes conjugated highpolymer, suitable conjugated highpolymer has polyfluorene (polyfluorene), poly-spiral shell-difluorene (poly (spiro-bifluorene)), poly-indenofluorene (polyindenofluorene), poly-(p-phenylene vinylene) (poly (p-phenylen-vinylene)), poly-(to phenylene) (poly (para-phenylene)), extremely derivative.
The invention still further relates to a composition, wherein include at least one according to compound of the present invention, at least one organic solvent.The example of organic solvent, includes, but is not limited to, methyl alcohol, ethanol, 2-methyl cellosolve, methylene dichloride, trichloromethane, chlorobenzene, orthodichlorobenzene, tetrahydrofuran (THF), methyl-phenoxide, morpholine, toluene, o-Xylol, m-xylene, p-Xylol, Isosorbide-5-Nitrae dioxane, acetone, methyl ethyl ketone, 1,2 ethylene dichloride, 3-phenoxytoluene, 1,1,1-trichloroethane, 1,1,2,2-tetrachloroethane, vinyl acetic monomer, N-BUTYL ACETATE, dimethyl formamide, N,N-DIMETHYLACETAMIDE, dimethyl sulfoxide (DMSO), naphthane, naphthalane, indenes and/or their mixture.
In a preferential embodiment, be a solution according to composition of the present invention.
In another embodiment, be a suspension according to composition of the present invention.
Composition of the present invention can comprise 0.01 to 20wt%, preferably 0.1 to 15wt%, more preferably 0.2 to 10wt%, most preferably the organic functional material of 0.25 to 5wt%.Described percent data relates to solvent or the solvent mixture of 100%.
The invention still further relates to described composition as coating or printing-ink the purposes when preparing organic electronic devices, the preparation method that preferential is especially by printing or being coated with.
The printing be applicable to or coating technique include, but is not limited to spray ink Printing, letterpress, silk screen printing, dip-coating, rotary coating, scraper for coating, roller printing, torsion roller printing, lithography, flexographic printing, rotary printing, spraying, brushes or bat printing, slit-type extruding type coating etc.It is preferred that both intaglio printing, silk screen printing and ink jet printing.Intaglio printing, ink jet printing will be applied in an embodiment of the present invention.Solution or suspension can comprise one or more component such as surface active cpd, lubricant, wetting agent, dispersion agent, hydrophobizing agent, caking agent etc. in addition, and for adjusting viscosity, film forming properties, improves tack etc.Relevant printing technique, and to the related request about solution, as solvent and concentration, viscosity etc., details refer to Helmut Kipphan edit " print media handbook: technology and production method " (Handbook of Print Media:Technologies and Production Methods), ISBN3-540-67326-1.
The invention further relates to an organic electronic devices, include one or more layers organic functional thin film, wherein have at least thin film to include according to compound of the present invention.
Suitable organic electronic devices includes but not limited to Organic Light Emitting Diode, organic light emission battery, organic photovoltaic battery, organic field-effect tube, organic light-emitting field effect pipe, organic sensor and organic phasmon emitting diode (Organic Plasmon EmittingDiode).Preferred organic electronic devices has Organic Light Emitting Diode, organic light emission battery.
In above-described luminescent device, comprise a substrate, an anode, at least one luminescent layer, a negative electrode.Substrate can be opaque or transparent.Transparent substrate can be used for the transparent emitting components of manufacture one.Such as can be see, the Nature1996 such as Bulovic, 380, p29, and Gu etc., Appl.Phys.Lett.1996,68, p2606.Base material can be rigidity or elastic.Substrate can be plastics, metal, semiconductor wafer or glass.Preferably substrate has a level and smooth surface.The substrate of free of surface defects is selection desirable especially.In a preferential embodiment, substrate is optional in polymeric film or plastics, and its second-order transition temperature Tg is more than 150 DEG C, is better above 200 DEG C, is more preferably more than 250 DEG C, preferably more than 300 DEG C.The example of suitable substrate has poly-(ethylene glycol terephthalate) (PET) and polyoxyethylene glycol (2,6-naphthalene) (PEN).
Anode can comprise a conducting metal or metal oxide, or conductive polymers.Anode can easily injected hole in HIL or HTL or luminescent layer.In the embodiment of, inorganic semiconductor twinkler or be less than 0.5eV as the absolute value of the HOMO energy level of the p-type semiconductor material of HIL or HTL or EBL or the difference of valence-band level in the work function of anode and luminescent layer, be better be less than 0.3eV, be preferably less than 0.2eV.The example of anode material includes but 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 are known, and those of ordinary skill in the art can easily choice for use.Anode material can use any suitable deposition techniques, as a suitable physical vaporous deposition, comprises rf magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam) etc.
In certain embodiments, anode is patterning.The ITO electrically-conductive backing plate of patterning can commercially have been bought, and can be used for preparation according to device of the present invention.
Negative electrode can comprise a conducting metal or metal oxide.Negative electrode easily can inject electronics to EIL or ETL or directly to luminescent layer.In the embodiment of, inorganic semiconductor twinkler or be less than 0.5eV as the absolute value of the lumo energy of the n-type semiconductor of EIL or ETL or HBL or the difference of conduction level in the work function of negative electrode and luminescent layer, be better be less than 0.3eV, be preferably less than 0.2eV.In principle, all materials that can be used as the negative electrode of OLED all may as the cathode material of device of the present invention.The example of cathode material includes but not limited to, Al, Au, Ag, Ca, Ba, Mg, LiF/Al, MgAg alloy, BaF 2/ Al, Cu, Fe, Co, Ni, Mn, Pd, Pt, ITO etc.Cathode material can use any suitable deposition techniques, as a suitable physical vaporous deposition, comprises rf magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam) etc.
In a preferential embodiment, according in luminescent device of the present invention, its luminescent layer is prepared from by printing note inventive composition.
The invention still further relates to according to luminescent device of the present invention application in electronic equipment of various, include, but not limited to display equipment, set lights, light source, sensor etc.
The invention still further relates to the electronics included according to luminescent device of the present invention, include, but not limited to display equipment, set lights, light source, sensor etc.
Some more detailed descriptions (but being not limited thereto) are done to organic functional material below.In principle, all organic functional materials for OLEDs, comprise hole (also claiming electric hole) to inject or transport material (HIM/HTM), hole barrier materials (HBM), electron injection or transport material (EIM/ETM), electron-blocking materials (EBM), organic host materials (Host), singlet emitters (fluorescent illuminant), heavy state twinkler (phosphorescent emitter), particularly luminescent organometallic complex compound, dyestuff (Dye), in luminescent device all used in the present invention.Such as in WO2010135519A1, US20090134784A1 and WO2011110277A1, various organic functional material is described later in detail, hereby the full content in this 3 patent document is incorporated to herein as a reference.
1.HIM/HTM
The suitable optional compound including following structural unit of organic HTM material: phthalocyanine (phthlocyanine), porphyrin (porphyrine), amine (amine), aromatic amine, biphenyl class triaryl amine (triarylamine), thiophene (thiophene), thiophthene (fused thiophene) is as two thienothiophenes (dithienothiophene) and thiophthene (dibenzothiphene), pyrroles (pyrrole), aniline (aniline), carbazole (carbazole), indolocarbazole (indolocarbazole), and their derivative.The suitable HTM of another position also comprises the polymkeric substance containing fluorohydrocarbon (fluorohydrocarbon); Polymkeric substance containing conductiving doping; Conductive polymers, as PEDOT/PSS; Self-assembly monomer, as the compound containing phosphonic acids and sliane derivative; Metal oxide, as MoOx; Metal complex, and cross-linking compounds etc.
The example that can be used as the fragrant amine derivative compounds of cyclophane of HIM or HTM includes, but is not limited to following general structure:
Each Ar 1to Ar 9can independently be selected from aromatic hydrocarbon ring compound, as benzene, biphenyl, triphenyl, benzo, naphthalene, anthracene, phenalene, luxuriant and rich with fragrance, fluorenes, pyrene, Qu ， perylene, Azulene, heteroaromatic compound, as dibenzothiophene, diphenylene-oxide, furans, thiophene, cumarone, thionaphthene, carbazole, pyrazoles, imidazoles, triazole, isoxzzole, thiazole, oxadiazoles, oxatriazole, dioxazole, thiadiazoles, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazines, oxathiazine, oxadiazine, indoles, benzoglyoxaline, indazole, indoxazine, benzoxazoles, benzisoxazole, benzothiazole, quinoline, isoquinoline 99.9, cinnoline, quinazoline, quinoxaline, naphthalene, phthalein, pteridine, xanthene, acridine, azophenlyene, thiodiphenylamine, Phenazoxine, dibenzoselenophene, benzoselenophene, benzofuropyridine, indolocarbazole, pyridylindole, pyrrolodipyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine and selenophenodipyridine, include the group of 2 to 10 ring structures, they can be aromatic hydrocarbon ring group or the aromatic heterocycle group of identical or different type, and directly or by least one following group link together each other, as Sauerstoffatom, nitrogen-atoms, sulphur atom, Siliciumatom, phosphorus atom, boron atom, chain structure unit and aliphatic cyclic group.Wherein, each Ar can be substituted further, and substituting group is chosen as hydrogen, alkyl, alkoxyl group, amino, alkene, alkynes, aralkyl, assorted alkyl, aryl and heteroaryl.
In one aspect, Ar 1to Ar 9independently can be selected from the group comprising following group:
N is the integer of 1 to 20; X 1to X 8cH or N; Ar 1aryl or heteroaryl.
The other example of the fragrant amine derivative compounds of cyclophane can see 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, has the nucleidic mass being greater than 40;
(Y 1-Y 2) be one or two tooth part, Y 1and Y 2independently selected from C, N, O, P, and S; L is an assistant ligand; M is an integer, and its value is from 1 to the maximum coordination number of this metal; M+n is the maximum coordination number of this metal.
In one embodiment, (Y 1-Y 2) be a 2-phenylpyridine derivative.
In another embodiment, (Y 1-Y 2) be a carbenes.
In another embodiment, M selects in Ir, Pt, Os, and Zn.
In yet another aspect, the HOMO of metal complex is greater than-5.5eV (relative to vacuum level).
The suitable example that can be used as HIM/HTM compound is listed in table below:
2.EIM/ETM
In principle, suitable N-shaped organic semiconductor material is optional in all EIM/ETM for OLEDs.The example of EIM/ETM material is not particularly limited, and any metal complex or organic compound all may be used as ETM, as long as they can transmission electronic.Preferential organic ETM material can be selected from three (oxine) aluminium (AlQ 3), azophenlyene (Phenazine), phenanthroline (Phenanthroline), anthracene (Anthracene), luxuriant and rich with fragrance (Phenanthrene), fluorenes (Fluorene), two fluorenes (Bifluorene), spiral shell two fluorenes (Spiro-bifluorene), to phenylacetylene (Phenylene-vinylene), triazine (triazine), triazole (triazole), imidazoles (imidazole), pyrene (Pyrene), perylene (Perylene), anti-indenofluorene (trans-Indenofluorene), along indeno (cis-Indenonfluorene), dibenzo-indenofluorene (Dibenzol-indenofluorene), indeno naphthalene (Indenonaphthalene), benzanthrene (benzanthracene) and their derivative.
On the other hand, the compound that can be used as EIM/ETM is the molecule at least comprising less than one group:
R 1optional in following group: hydrogen, alkyl, alkoxyl group, amino, alkene, alkynes, aralkyl, assorted alkyl, aryl and heteroaryl, when they be aryl or heteroaryl time, the Ar in they and above-mentioned HTM 1and Ar 2same meaning;
Ar 1-Ar 5with the Ar described in HTM 1same meaning;
N be one from 0 to 20 integer;
X 1-X 8select in CH or N, wherein have at least one to be 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) be one or two tooth part, wherein metal and O, N or N, N coordination; L is an assistant ligand; M is an integer, and its value is from 1 to the maximum coordination number of this metal.
In the embodiment that another is preferential, organic alkali metal compound can be used as EIM.In the present invention, organic alkali metal compound is appreciated that the compound dug as following, wherein has basic metal, i.e. a lithium at least, sodium, potassium, rubidium, caesium, and comprises at least one organic ligand further.
Suitable organic alkali metal compound, comprises US7767317B2, the compound described in EP1941562B1 and EP1144543B1.
The organic alkali metal compound of prioritizing selection is the compound of following chemical formula:
Wherein R 1implication described above, camber line represents two or three atoms and keyed jointing, so as if desired form 5 yuan or six-ring with metal M, its Atom also can by one or more R 1replace, M is basic metal, is selected from lithium, sodium, potassium, rubidium, caesium.Organic alkali metal compound can have the form of monomer, as previously discussed, or has the form of aggregate, such as, and two alkalimetal ions and two parts, 4 alkalimetal ions and 4 parts, 6 alkalimetal ions and 6 parts or the form at other.
The organic alkali metal compound of special prioritizing selection is the compound of following chemical formula:
The symbol wherein used is identical with aforementioned definitions, in addition: M is alkali metal
O, can be identical or different when occurring, be 0,1,2,3 or 4 at every turn;
P, can be identical or different when occurring, be 0,1,2 or 3 at every turn;
In a preferential embodiment, basic metal M is selected from lithium, sodium, potassium, is more preferably lithium or sodium, preferably lithium.
In a preferential embodiment, in organic alkali metal compound electron injecting layer. better, electron injecting layer is made up of organic alkali metal compound.
In the embodiment that another is preferential, organic alkali metal compound is doped in other ETM and is formed in electron transfer layer or electron injecting layer. and better, be electron transfer layer.
The example of suitable organic alkali metal compound is listed in table below:
3. triplet state substrate material (Triplet Host):
The example of triplet state substrate material is not particularly limited, and any metal complex or organic compound all may be used as matrix, as long as its triplet energies is than twinkler, particularly triplet emitters or phosphorescent emitter higher.
The example that can be used as the metal complex of triplet state matrix (Host) includes, but is not limited to following general structure:
M is a metal; (Y 3-Y 4) be one or two tooth part, Y 3and Y 4independently selected from C, N, O, P, and S; L is an assistant ligand; M is an integer, and its value is from 1 to the maximum coordination number of this metal; M+n is the maximum coordination number of this metal.
In a preferential embodiment, the metal complex that can be used as triplet state matrix has following form:
(O-N) be one or two tooth part, wherein metal and O and atom N coordination.
In some embodiments, M is optional in Ir and Pt.
The example that can be used as the organic compound of triplet state matrix is selected from the compound including aromatic hydrocarbon ring base, hinders as benzene, biphenyl, triphenyl, benzo, fluorenes, test, include the compound of fragrant heterocyclic radical, as dibenzothiophene, diphenylene-oxide, dibenzoselenophene, furans, thiophene, cumarone, thionaphthene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazoles, imidazoles, triazole species, oxazole, thiazole, oxadiazoles, oxatriazole, dioxazole, thiadiazoles, pyridine, pyridazine, pyrimidine, pyrazine, triazines, oxazines, oxathiazines, oxadiazines, indoles, benzoglyoxaline, indazole, indoxazine, bisbenzoxazoles, benzisoxazole, benzothiazole, quinoline, isoquinoline 99.9, cinnoline, quinazoline, quinoxaline, naphthalene, phthalein, pteridine, xanthene, acridine, azophenlyene, thiodiphenylamine, phenoxazines, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine and selenophenodipyridine, include the group of 2 to 10 ring structures, they can be aromatic hydrocarbon ring group or the aromatic heterocycle group of identical or different type, and directly or by least one following group link together each other, as Sauerstoffatom, nitrogen-atoms, sulphur atom, Siliciumatom, phosphorus atom, boron atom, chain structure unit and aliphatic cyclic group.Wherein, each Ar can be substituted further, and substituting group is chosen as hydrogen, alkyl, alkoxyl group, amino, alkene, alkynes, aralkyl, assorted alkyl, aryl and heteroaryl.
In a preferential embodiment, triplet state substrate material is optional in the compound comprising at least one following group:
R 1-R 7can select independently of each other in following group: hydrogen, alkyl, alkoxyl group, amino, alkene, alkynes, aralkyl, assorted alkyl, aryl and heteroaryl, when they be aryl or heteroaryl time, the Ar in they and above-mentioned HIM/HTM 1and Ar 2same meaning; N be one from 0 to 20 integer; X 1-X 8select in CH or N; X 9select in CR 1r 2or NR 1.
4. singlet state substrate material (Singlet Host):
The example of singlet state substrate material is not particularly limited, and any organic compound all may be used as matrix, as long as its singlet energy is than twinkler, particularly singlet emitters or fluorescent illuminant higher.
Example as the organic compound of singlet state substrate material use is optional from containing aromatic hydrocarbon ring compound, as benzene, and biphenyl, triphenyl, benzo, naphthalene, anthracene, phenalene, luxuriant and rich with fragrance, fluorenes, pyrene, bends, perylene, Azulene, heteroaromatic compound, as dibenzothiophene, diphenylene-oxide, dibenzoselenophene, furans, thiophene, cumarone, thionaphthene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, Pyrrolodipyridine, pyrazoles, imidazoles, triazole, isoxzzole, thiazole, oxadiazoles, oxatriazole, dioxazole, thiadiazoles, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazines, oxathiazine, oxadiazine, indoles, benzoglyoxaline, indazole, indoxazine, benzoxazoles, benzisoxazole, benzothiazole, quinoline, isoquinoline 99.9, cinnoline, quinazoline, quinoxaline, naphthalene, phthalein, pteridine, xanthene, acridine, azophenlyene, thiodiphenylamine, Phenazoxine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine and selenophenodipyridine, include the group of 2 to 10 ring structures, they can be aromatic hydrocarbon ring group or the aromatic heterocycle group of identical or different type, and directly or by least one following group link together each other, as Sauerstoffatom, nitrogen-atoms, sulphur atom, Siliciumatom, phosphorus atom, boron atom, chain structure unit and aliphatic cyclic group.
In a preferential embodiment, singlet state substrate material is optional in the compound comprising at least one following group:
R 1-R 7can select independently of each other in following group: hydrogen, alkyl, alkoxyl group, amino, alkene, alkynes, aralkyl, assorted alkyl, aryl and heteroaryl, when they be aryl or heteroaryl time, they and above-mentioned Ar 1and Ar 2same meaning;
N be one from 0 to 20 integer; X 1-X 8select in CH or N; X 9, X 10select in CR 1r 2or NR 1.
5. hole barrier materials (HBM)
Hole blocking layer (HBL) is commonly used to stop from successive functional layers, the particularly hole of luminescent layer.Contrast the OLED that does not have blocking layer, the existence of HBL can cause the raising of luminous efficiency usually.The hole barrier materials (HBM) of hole blocking layer (HBL) needs and compares successive functional layers, HOMO. as lower in luminescent layer is in a preferential embodiment, HBM has the excited level larger than adjacent emissive layers, as singlet state or triplet state, depend on twinkler. in the embodiment that another is preferential, HBM has electric transmission function.
In the embodiment of, contain the molecule identical with luminescent layer mesostroma material as HBM.
In the embodiment that another is preferential, HBM is optional in the compound comprising at least one following group:
N be one from 0 to 20 integer; L is an assistant ligand; M be one from 1 to 3 integer.
6. singlet emitters (Singlet Emitter)
Singlet emitters often has longer conjugated pi electron system.So far, existing many examples, such as styrylamine (styrylamine) and derivative thereof disclosed in JP2913116B and WO2001021729A1, and disclosed in WO2008/006449 and WO2007/140847 indenofluorene (indenofluorene) and derivative thereof.
In a preferential embodiment, singlet emitters can be selected from unitary styrylamine (monostyrylamines), binary styrylamine (distyrylamines), ternary styrylamine (tristyrylamines), quaternary styrylamine (tetrastyrylamines), vinylbenzene phosphine (styrylphosphines), vinylbenzene ether (styryl ethers) and arylamine (arylamines).
A unitary styrylamine refers to a compound, and it comprises one without the styryl group replaced or replace and at least one amine, preferably aromatic amine.A binary styrylamine refers to a compound, and it comprises two without the styryl group replaced or replace and at least one amine, preferably aromatic amine.A ternary styrylamine refers to a compound, and it comprises three without the styryl group replaced or replace and at least one amine, preferably aromatic amine.A quaternary styrylamine refers to a compound, and it comprises four without the styryl group replaced or replace and at least one amine, preferably aromatic amine.A preferred vinylbenzene is toluylene, and it may be substituted further.Corresponding phosphine class is similar to amine with the definition of ethers.Arylamines or aromatic amine refer to a kind of compound, the aromatic nucleus that the nothing comprising three direct connection nitrogen replaces or replaces or heterocyclic ring system.Have at least one preferentially to select in carbocyclic fused ring system in the loop systems of these aromatic series or heterocycle, and preferably have at least 14 aromatic ring atoms.Wherein preferred example has fragrant anthranylamine, fragrant anthradiamine, fragrant pyrene amine, fragrant pyrene diamines, and fragrance bends amine and fragrance bends diamines.A fragrant anthranylamine refers to a compound, and one of them binary arylamines group (diarylamino) is directly linked on anthracene, preferably on the position of 9.A fragrant anthradiamine refers to a compound, and wherein two binary arylamines groups (diarylamino) are directly linked on anthracene, preferably 9, on the position of 10.Fragrance pyrene amine, fragrant pyrene diamines, the definition that fragrance amine in the wrong and fragrance bend diamines is similar, and wherein binary arylamines group is preferably linked to 1 or 1 of pyrene, on 6 positions.
Based on the example of the singlet emitters of vinyl-amine and arylamine, also be preferred example, can find in following patent document: WO2006/000388, WO2006/058737, WO2006/000389, WO2007/065549, WO2007/115610, US7250532B2, DE102005058557A1, CN1583691A, JP08053397A, US6251531B1, US2006/210830A, EP1957606A1 and the US2008/0113101A1 full content hereby in the above-mentioned patent document listed is incorporated to herein as a reference.
Example based on stibene (distyrylbenzene) the extremely singlet emitters of derivative has US5121029.
Further preferred singlet emitters is optional in indenofluorene-amine and indenofluorene-diamines, disclosed in WO2006/122630, benzo indenofluorene-amine (benzoindenofluorene-amine) and benzo indenofluorene-diamines (benzoindenofluorene-diamine), disclosed in WO2008/006449, dibenzo indenofluorene-amine (dibenzoindenofluorene-amine) and dibenzo indenofluorene-diamines (dibenzoindenofluorene-diamine), disclosed in WO2007/140847.
Other materials that can be used as singlet emitters have polycyclic aromatic hydrocarbon compounds, the particularly derivative of following compound: anthracene is as 9, 10-bis-(2-naphthanthracene) (9, 10-di (2-naphthylanthracene)), naphthalene, four benzene, xanthene, luxuriant and rich with fragrance (phenanthrene), pyrene (perylene) is as 2, 5, 8, 11-tetra-t-butylperylene, indeno pyrene (indenoperylene), penylene (phenylenes) is as (4, 4 '-(bis (9-ethyl-3-carbazovinylene)-1, 1 '-biphenyl), periflanthene, decacyclene (decacyclene), coronene (coronene), fluorenes, spiral shell two fluorenes (spirofluorene), aryl pyrene (arylpyrene) (as US20060222886), arylene ethene (arylenevinylene) is (as US5121029, US5130603), cyclopentadiene is as tetraphenyl cyclopentadiene (tetraphenylcyclopentadiene), rubrene (rubrene), tonka bean camphor (coumarine), rhodamine (rhodamine), quinacridone (quinacridone), pyrans (pyrane) is as 4
(dicyanoethylene)-6-(4-dimethylaminostyryl-2-methyl)-4H-pyrane (DCM), thiapyran (thiapyran), bis (azinyl) imine-boron compound (US2007/0092753A1), bis (azinyl) methene compound, carbostyryl compound oxazinone (oxazone), benzoxazoles (benzoxazole), benzothiazole (benzothiazole), benzoglyoxaline (benzimidazole) and diketopyrrolopyrrole.The material of some singlet emitters can find in following patent document: US20070252517A1, US4769292, US6020078, US2007/0252517A1, US2007/0252517A1.Hereby the full content in the above-mentioned patent document listed is incorporated to herein as a reference.
7. triplet emitters (Triplet Emitter)
Triplet emitters also claims phosphorescent emitter.In a preferential embodiment, triplet emitters is the metal complex having formula M (L) n, and wherein M is an atoms metal, can be identical or different when L occurs at every turn, it is an organic ligand, it is connected on atoms metal M by one or more positions keyed jointing or coordination, and n is an integer being greater than 1, and better choosing is 1,2,3,4,5 or 6.Alternatively, these metal complexs are connected on a polymkeric substance, preferably by organic ligand by one or more position.
In a preferential embodiment, atoms metal M selects in transition metal or lanthanon or actinide elements, prioritizing selection Ir, Pt, Pd, Au, Rh, Ru, Os, Sm, Eu, Gd, Tb, Dy, Re, Cu or Ag, special prioritizing selection Os, Ir, Ru, Rh, Re, Pd, Pt.
Preferentially, triplet emitters includes chelating ligand, i.e. part, and by least two basic change point and metal-complexing, what give special priority for is that triplet emitters includes two or three identical or different bidentate or polydentate ligands.Chelating ligand is conducive to the stability improving metal complex.
The example of organic ligand can be selected from phenylpyridine (phenylpyridine) derivative, 7,8-benzoquinoline (7,8-benzoquinoline) derivative, 2 (2-thienyl) pyridine (2 (2-thienyl) pyridine) derivative, 2 (1-naphthyl) pyridine (2 (1-naphthyl) pyridine) derivative, or 2 phenylquinolines (2phenylquinoline) derivative.All these organic ligands all may be substituted, such as, replaced by fluorine-containing or trifluoromethyl.Assistant ligand preferentially can be 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, selects in transition metal or lanthanon or actinide elements;
Ar 1can be identical or different at every turn when occurring, be a cyclic group, wherein at least include a donor atom, namely have the atom of lone-pair electron, as nitrogen or phosphorus, be connected with metal-complexing by its cyclic group; Ar 2can be identical or different at every turn when occurring, be a cyclic group, wherein at least include a C atom, be connected with metal by its cyclic group; Ar 1and Ar 2be connected together by covalent bond, can carry one or more substituted radical separately, they also can be linked together by substituted radical again; Can be identical or different at every turn when L occurs, be an assistant ligand, be preferable over double-tooth chelate ligand, preferably monoanionic, bidentate chelating ligand; M is 1,2 or 3, is preferentially 2 or 3, is especially preferentially 3; N is 0,1, or 2, being preferentially 0 or 1, is especially preferentially 0.
The example that the material of some triplet emitters is extremely applied can find in following patent document and document: WO200070655, WO200141512, WO200202714, WO200215645, EP1191613, EP1191612, EP1191614, WO2005033244, WO2005019373, US2005/0258742, WO2009146770, WO2010015307, WO2010031485, WO2010054731, WO2010054728, WO2010086089, WO2010099852, WO2010102709, US20070087219A1, US20090061681A1, US20010053462A1, Baldo, Thompson et al.Nature403, (2000), 750-753, US20090061681A1, US20090061681A1, 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, US2007/0252517A1, Johnson et al., JACS105, 1983, 1795, Wrighton, JACS96, 1974, 998, Ma et al., Synth.Metals94, 1998, 245, US6824895, US7029766, US6835469, US6830828, US20010053462A1, WO2007095118A1, US2012004407A1, WO2012007088A1, WO2012007087A1, WO2012007086A1, US2008027220A1, WO2011157339A1, CN102282150A, WO2009118087A1.Hereby the full content in the above-mentioned patent document listed and document is incorporated to herein as a reference.
8. dyestuff (Dye)
In principle, all for organic photovoltaic battery, comprise DSSC, organic functions dyestuff, in electron device all used in the present invention.Suitable dyestuff is selected from the multi-pyridine ligand of transition metal, preferred ruthenium, osmium, the metal complex dyes of copper.In a preferred embodiment, the general structure ML2 (X) 2 of metal complex dyes, wherein L is preferentially selected from 2, in 2'-dipyridyl-4,4'-dicarboxylic acid, M is transition metal, excellent dyestuff is selected from Ru, Os, Fe, V and Cu, X is selected from halogenide, prussiate, thiocyanate-, acetylacetonate compound, the substituting group of thiocarbamate or water.These metallized dyes are disclosed The Journal of Physical Chemistry C2009 in the following literature, 113,2966-2973, US2009000658, WO2009107100, WO2009098643, US6245988, WO2010055471, JP2010084003, EP1622178, WO9850393, WO9529924, WO9404497, WO9214741, WO9116719.Hereby the full content in the above-mentioned patent document listed and document is incorporated to herein as a reference.
Describe the present invention below in conjunction with preferred embodiment, but the present invention is not limited to following embodiment, be to be understood that, claims it should be appreciated by one skilled in the art that under summarising the guiding that scope of the present invention conceives in the present invention, to certain change that various embodiments of the present invention are carried out, all by cover by the spirit and scope of claims of the present invention.
Embodiment
1. the synthesis of compound F 17-hydroxy-corticosterone 1-F4
General synthesis path, under room temperature (300K), the negatively charged ion of carbazole with fluoridize cyano group boron azane and react 16 hours under nitrogen atmosphere.Products therefrom carries out purifying by column chromatography on silica gel, redeposition.Before light-metering photoluminescence and electroluminescent spectrum, the further sublimation purification of compound.
2. the energy-structure of compound F 17-hydroxy-corticosterone 1-F4
The energy-structure of compound F 17-hydroxy-corticosterone 1-F4 obtains by quantum calculation, and such as utilize TD-DFT (time-depentent DFT) by Gaussian03W (Gaussian Inc.), concrete analogy method can see WO2011141110.First use semi-empirical approach " Ground State/Semi-empirical/Default Spin/AM1 " (Charge0/Spin Singlet) to optimize molecular geometry, then the energy-structure of organic molecule calculates " TD-SCF/DFT/Default Spin/B3PW91 " and base group " 6-31G (d) " (Charge0/Spin Singlet) by TD-DFT (time-depentent DFT) method.HOMO and lumo energy calculate according to calibration equation below, S1 and T1 directly uses.
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 calculation result of Gaussian03W, and unit is Hartree.Result is 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
Wherein Δ (S1-T1)≤the 0.10eV of F1, F2, F3.
3. photoluminescence spectra
F1, F2, F3 photoluminescence spectra records in toluene.The peak value of F1 roughly 416nm, F2 peak value roughly at the peak value of 407nm, F3 roughly at 404nm.
The preparation of 4.OLEDs and measurement
Following material of main part H1 is used as material of main part of the present invention.The synthesis of H1 can see Appl.Phys.Lett.Vol88, and 183503 and reference.The T1 of H1 is higher than the S1 of F1, F2, F3.
OLEDs vacuum evaporation forms, and its structure is as follows:
ITO(50nm)/NPD(40nm)/H1:Fx(5wt％)(15nm)/TPBi(65nm)/LiF(1nm)/Al(100nm)
Current/voltage (I-V) characteristic of OLED carrys out record by computer-controlled (Keithley2400source measurement unit) and (Keithley2000multimeter), simultaneously, brightness is measured by using the silicon photoelectric diode (Newport2112) calibrated.Electroluminescent spectrum is measured by spectrograph (Ocean Optics USB2000).OLED1-3, under the voltage of more than 3V, sends out light dark blue, and their performance is summarised in table 2 below, and wherein EQE (External Quantum Efficiency) represents external quantum efficiency.The EQE of all OLED1-3 all more than 9%, 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. the compound according to following general formula 0:
Wherein: D is electron-donating group, A is electron withdrawing group, and core B is a group including borazine, and m, n are the integer of 1-6.
2. compound according to claim 1, its center B is selected from the group including following structure:
Wherein any two H can be replaced by electron withdrawing group A or electron-donating group D or other groups.
3. compound according to claim 1, has following general formula 1:
Wherein: R 1-R 6independently be selected from hydrogen atom, phenyl ring, electron-donating group, electron withdrawing group or other substituting groups, but have at least one to be selected from electron-donating group, have at least one to be selected from electron withdrawing group.
4. according to the one or more described compound in claim 1-3, wherein
1) electron-donating group D is selected from the group including arbitrary skeleton in following general formula D 1-D30:
2) electron withdrawing group A is selected from the group including arbitrary skeleton in following general formula A1-A25
In a preferential embodiment, the electron withdrawing group described in general formula 1 is selected from cyano group or includes following group:
5. according to the one or more described compound in claim 1-4, its Δ (S1-T1)≤0.30eV.
6. a mixture, include a kind of according to the one or more described compound in claim 1-5, with another organic functional material, organic functional material is selected from hole and injects or transport material (HIM/HTM), hole barrier materials (HBM), electron injection or transport material (EIM/ETM), electron-blocking materials (EBM), organic host materials (Host), singlet emitters (fluorescent illuminant), triplet emitters (phosphorescent emitter), particularly luminescent organometallic complex compound, and dyestuff etc.
7. a composition, includes at least one according to the one or more described compound in claim 1-5 or at least one according to the mixture described in claim 6, and at least one organic solvent.
8. according to the one or more described application of compound in organic electronic devices in claim 1-5, organic electronic devices includes OLED, organic light emission battery, organic photovoltaic battery, organic field-effect tube, organic light-emitting field effect pipe, organic sensor and organic phasmon emitting diode (Organic Plasmon Emitting Diode).
9. an organic electronic devices, at least includes a kind of according to the one or more described compound in claim 1-5.
10. organic electronic devices according to claim 9, optional from Organic Light Emitting Diode, organic light emission battery, organic photovoltaic battery, organic field-effect tube, organic light-emitting field effect pipe, organic sensor and organic phasmon emitting diode (Organic Plasmon Emitting Diode).
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