CN105226193A - A kind of electroluminescent device including fused ring compound and metal organic complex - Google Patents

A kind of electroluminescent device including fused ring compound and metal organic complex Download PDF

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CN105226193A
CN105226193A CN201510346813.0A CN201510346813A CN105226193A CN 105226193 A CN105226193 A CN 105226193A CN 201510346813 A CN201510346813 A CN 201510346813A CN 105226193 A CN105226193 A CN 105226193A
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electroluminescent device
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CN105226193B (en
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潘才法
其他发明人请求不公开姓名
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Zhejiang Brilliant Optoelectronic Technology Co Ltd
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/371—Metal complexes comprising a group IB metal element, e.g. comprising copper, gold or silver
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Abstract

The present invention is a kind of electroluminescent device including fused ring compound and metal organic complex, relate to a kind of novel electroluminescent device comprising a material of main part and metal organic complex, wherein the ground state spin quantum number of material of main part is 1, and Δ (S1-T1) >=0.75eV, the spin quantum number of the ground state of metal complex is 2.Particularly Organic Light Emitting Diode, light emitting electrochemical cell, thus be for display device, the technology in illumination and other occasions adds a kind of option.The preparation method also relating to this electroluminescent device of the present invention, particularly based on the preparation method of solution. the various application that this electroluminescent device is also provided of the present invention.

Description

A kind of electroluminescent device including fused ring compound and metal organic complex
Art:
The present invention relates to a kind of electroluminescent device including fused ring compound and metal organic complex, particularly Organic Light Emitting Diode, and device architecture, its production method and the application in illumination and Display Technique and other occasions thereof.
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 chemical synthesis to color, flexible etc. become current most promising next generation's display and lighting technology.Particularly they can by the method printed, as inkjet printing (InkJetPrinting), technology film forming from solution such as silk screen printing (ScreenPrinting), 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.Current high efficiency OLED is generally realized by phosphorescent light-emitting materials, but is only limited to green glow and ruddiness phosphorescent OLED, and the blue emitting phosphor OLED of stability and high efficiency does not also realize.This is because except lacking stable blue emitting phosphor luminescent material, corresponding material of main part must have very strategic hinterland areas of China's state energy level, otherwise the triplet excitons on blue emitting phosphor luminescent material can be transferred in main body and produces quenching effect; Simultaneously adjacent with luminescent layer hole transmission layer (HTL), electron transfer layer (ETL), or exciton barrier-layer (ExBL) also must have the triplet larger than blue light phosphorescent emitter.This just makes to bring very large challenge to the design of material of these functional layers with synthesis.Material of main part for blue phosphor OLED is generally include fused ring compound, typical in the compound based on anthracene, the stability of this compounds is very good, but triplet is very low, during when the luminescent layer for phosphorescent OLED or in ETL or HTL that luminescent layer is adjacent, the luminescence of its meeting cancellation phosphorescent emitter.Therefore, people always wish, have new combination of materials or technology to occur, can make up the defect of prior art.
Summary of the invention
The invention provides a kind of novel electroluminescent device, comprise 1) luminescent layer, wherein at least comprise a material of main part, the spin quantum number of its ground state is 1, and Δ (S1-T1) >=0.75eV, with a metal complex, the spin quantum number of its ground state is 2; 2) positive electrode of functional layer side is arranged in; 3) negative electrode of functional layer opposite side is arranged in.Described electroluminescent device is optional from organic light emitting diode, quantum dot light emitting diode, light emitting electrochemical cell etc.Extend according to electroluminescent device of the present invention and can be used for display device, illumination and other occasions in technology option.Second object of the present invention is to provide the preparation method of this electroluminescent device, particularly based on the preparation method of solution. and the 3rd object of the present invention is to provide the various application of this electroluminescent device.
Accompanying drawing is sketched
Fig. 1 is according to a kind of emitting device structure of the present invention.101. substrates in figure, 102. anodes, 103.EML, 104. negative electrodes.
Fig. 2 is according to a kind of preferential emitting device structure figure of the present invention.201. substrates in figure, 202. anodes, 203.EML, 204. negative electrodes, 205.HIL or HTL or EBL or ExBL.
Fig. 3 is according to the preferential emitting device structure figure of another kind of the present invention.301. substrates in figure, 302. anodes, 303.EML, 304. negative electrodes, 305.EIL or ETL or HBL or ExBL.
Fig. 4 is according to a kind of preferential emitting device structure figure of the present invention.401. substrates in figure, 402. anodes, 403.EML, 404. negative electrodes, 405.EIL or ETL or HBL or ExBL, 406.HIL or HTL or EBL or ExBL.
Wherein HIL represents hole injection layer, and HTL represents hole transmission layer, and HBL represents hole blocking layer, and EIL represents electron injecting layer, and ETL represents electron transfer layer, and EBL represents electronic barrier layer, and EML represents luminescent layer, and ExBL represents exciton barrier-layer.
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, semiconductor device in detail at this, and nanocrystal, nano wire (NW), nanometer rods, nanotube and nanoribbon technologies, relevant organic material, and other function of system.
The invention provides a kind of novel electroluminescent device, comprise
1) luminescent layer, wherein at least comprises a material of main part, and the spin quantum number of its ground state is 1, and Δ (S1-T1) >=0.75eV, and a metal complex, the spin quantum number of its ground state is 2;
2) positive electrode of functional layer side is arranged in;
3) negative electrode of functional layer opposite side is arranged in.
Wherein S1 is singlet energy level, and T1 is triplet.
In a general embodiment, there is the structure chart shown in Fig. 1 according to luminescent device of the present invention, include substrate (101), anode (102), luminescent layer (103), negative electrode (104).Substrate (101) also can be positioned at the side of negative electrode (104).In kind of device, functional layer only has luminescent layer.
Preferably, according to luminescent device of the present invention, also include other functional layers.
In a preferential embodiment, the structure chart shown in Fig. 2 is had according to luminescent device of the present invention, include substrate (201), anode (202), luminescent layer (203), negative electrode (204), and HIL or HTL between luminescent layer and anode or EBL or ExBL (205).Substrate (201) also can be positioned at the side of negative electrode (204).
In the embodiment that another is preferential, the structure chart shown in Fig. 3 is had according to luminescent device of the present invention, include substrate (301), anode (302), luminescent layer (303), negative electrode (304), and EIL or ETL between luminescent layer and negative electrode or HBL or ExBL (305).Substrate (301) also can be positioned at the side of negative electrode (304).
In the embodiment that another is preferential especially, the structure chart shown in Fig. 4 is had according to luminescent device of the present invention, include substrate (401), anode (402), luminescent layer (403), negative electrode (404), EIL or ETL between luminescent layer and negative electrode or HBL (405), and HIL or HTL between luminescent layer and anode or EBL or ExBL (406).Substrate (401) also can be positioned at the side of negative electrode (404).
The example of the structure according to luminescent device of the present invention possible is in addition, but be not limited to, anode/HIL/HTL/EML/ negative electrode, anode/HIL/HTL/EML/ETL/ negative electrode, anode/HIL/HTL/EML/ETL/EIL/ negative electrode, anode/HIL/HTL/EBL/EML/ETL/EIL/ negative electrode, anode/HIL/HTL/EBL/EML/ETL/ negative electrode, anode/HIL/HTL/EBL/EML1/EML2/ETL/EIL/ negative electrode, anode/EML/ETL/EIL/ negative electrode, anode/HIL/HTL/EBL/EML/HBL/ETL/EIL/ negative electrode etc.
In above-described device, the scope of the thickness of HIL or HTL or EBL or EML or ETL or EIL or ExBL from 5-1000nm, can be better 10-800nm, is more preferably 10-500nm, preferably 10-100nm.
Electroluminescent device refers to irradiative device under the effect of electric field.In certain embodiments, the emission wavelength range of electroluminescent device of the present invention from UV to near-infrared, preferably from 350nm to 850nm, better from 380nm to 800nm, preferably from 380nm to 680nm.
In a preferential embodiment, electroluminescent device of the present invention is Organic Light Emitting Diode OLED.
In general, in luminescent layer (EML), material of main part is the component occupied the majority.The ratio of luminous element in luminescent layer is 1-25wt%, is better 2-20wt%, is more preferably 3-15wt%, preferably 5-10wt%.
In one embodiment, luminescent layer also comprises another kind of host material.When the matrix of luminescent layer includes two kinds of host materials, both part by weight are be better 1:4 to 4:1, be more preferably 1:3 to 3:1, preferably 1:2 to 2:1 from 1:5 to 5:1.Can be wherein that a kind of inorganic material adds another kind of inorganic material, also can be that a kind of inorganic material adds another kind of organic material.Preferential combination is a kind of host material is p-type semiconductor, and another kind is n-type semiconductor.In the present invention, p-type semiconductor material, hole mobile material and HTM have identical implication, and they can exchange.N-type semiconductor electron transport material and ETM have identical implication, and they can exchange.
In certain embodiments, according in electroluminescent device of the present invention, luminescent layer comprises an ionic compound.This luminescent device also claims light emitting electrochemical cell.Known by the patent personnel that light emitting electrochemical cell is this area, can see Pei & Heeger, Science (1995), 269, pp1086-1088. ionic compound can be material of main part, luminescent material or the ionogenic compound of other conduct.In a preferential embodiment, light emitting electrochemical cell also includes ion transfer material.The ionic compound being suitable for light emitting electrochemical cell to various in WO2012013270A1, WO2012126566A1 and WO2012152366A1 and ion transfer material are described later in detail, and are hereby incorporated to herein as a reference by the full content in this 3 patent document.
In embodiments of the present invention, for the level structure of organic material, HOMO, LUMO, triplet (T1) and singlet energy level (S1), and the spin quantum number of ground state is that SOMO (singlyoccupiedMO), the LUMO of the metal organic complex of 2 plays a part key.Below the decision of these energy levels is made a presentation.HOMO, LUMO, SOMO energy level can be measured by photoelectric effect, such as XPS (x-ray photoelectron spectroscopy) and UPS (UV photoelectron spectroscopy) or by cyclic voltammetry (hereinafter referred to as CV).Recently, quantum chemical methods, such as density functional theory (hereinafter referred to as DFT), also become the method for effective calculating molecular orbital energy level.
The triplet T1 of organic material measures by low temperature time-resolved emission spectrometry, or obtained by quantum simulation calculating (as passed through Time-dependentDFT), as passed through business software Gaussian03W (GaussianInc.), concrete analogy method can see WO2011141110.The singlet energy level S1 of organic material, by absorption spectrum, or emission spectrum is determined, also calculates (as Time-dependentDFT) by quantum simulation and obtains.
It should be noted that HOMO, the absolute value of LUMO, SOMO, T1 and S1 depends on method of measurement used or computational methods, and even for identical method, the method for different evaluation, such as on CV curve, starting point and peak dot can provide different HOMO/LUMO values.Therefore, rationally significant comparison carry out with identical evaluation method by identical method of measurement.In the description of the embodiment of the present invention, the value of HOMO, LUMO, SOMO, T1 and S1 is the simulation based on Time-dependentDFT, but does not affect the application of other measurements or computational methods.
Suitable metal organic complex has chemical formula M (L) n, wherein M is transiting group metal elements or copper family elements, can be identical or different when L occurs at every turn, is an organic ligand, it is connected on metallic atom M by one or more positions keyed jointing or coordination, and n is an integer being greater than 1, and better choosing is 1, and 2,3,4,5 or 6.Alternatively, these metal complexs are connected on a polymer, preferably by organic ligand by one or more position.
In a preferential embodiment, metallic atom M selects in transition metal or lanthanide series or actinides, 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.
In the embodiment that another is very preferential, metallic element is selected from copper family elements, i.e. Au, Ag, Cu.
Preferentially, described metal organic complex includes cheland, 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 multidentate ligands.Cheland 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 phenylchinolines (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 more preferential embodiment, metallic element is Au.One preferably has following chemical formula (I) and (II) containing the metal organic complex of gold
Wherein A is the derivative of the circulus of a pyridine groups, the circulus of B and C to be B and C be phenyl derivatives, X is N, Y, Z is C or N, R1, R2 is a strong σ donor groups being connected to gold atom, or be the optional carbon donor ligand replaced, R1 and R2 arbitrarily can be combined into a bidentate ligand.
In a preferred embodiment, R1, R2 are groups including alkynyl.
The spin quantum number of suitable ground state is that the example of 2 metal organic complexes has
Usually, the suitable material of main part as main body of the present invention, the spin quantum number of its ground state is 1, and Δ (S1-T1) >=0.75eV, better Δ (S1-T1) >=0.85eV, be more preferably Δ (S1-T1) >=0.95eV, preferably Δ (S1-T1) >=1.0eV.
Suitable material of main part can select arbitrarily the organic compound in having large conjugated system.In certain embodiments, the conjugated system being greater than two stupid rings is had at least.
In a preferred embodiment, suitable material of main part is the group comprising following chemical formula (III):
Wherein
A,B 1, B 2independent of each otherly when multiple appearance be selected from a divalent group, be preferable over-CR 1r 2-,-NR 1-,-PR 1-,-O-,-S-,-SO-,-SO 2-,-CO-,-CS-,-CSe-,-P (=O) R 1-,-P (=S) R 1-,-SiR 1r 2-,-CR 1r 2-CR 3r 4-,-CR 1r 2-SiR 3r 4,-CR 1r 2-NR 3-,-CR 1r 2-O-,-CR 1r 2-NR 3-,-CR 1r 2-C (=O)-,-CR 1r 2-S-,-SiR 1r 2-NR 3-,-SiR 1r 2-O-,-SiR 1r 2-NR 3-,-SiR 1r 2-C (=O)-,-SiR 1r 2-S-,-CR 1=CR 1-,-CR 1=N-,-CR 1=CR 1-,-C ≡ C-,
R 1, R 2, R 1, R 2be identical or different group independent of each other, can select in H, halogen ,-CN ,-NC ,-NCO ,-NCS ,-OCN ,-SCN ,-C (=O) NR 0r 00,-C (=O) R 0,-NH 2,-NR 0r 00,-SH ,-SR 0,-SO 3h ,-SO 2r 0,-OH ,-NO 2,-CF 3,-SF 5, the optional silicyl replaced, or include alkyl or the carbonyl of 1 to 40 carbon atom, they can be optionally substituted, and optionally comprise one or more hetero-atom, R 0, R 00be alkyl or the carbonyl of hydrogen independent of each other or optional replacement, optionally comprise one or more hetero-atom group,
Every n is independently 0 or 1, with corresponding each h at same subunit be 0 or 1, m be the >=integer of 1.
Preferably according to the example of chemical formula (III), but be not limited to, as follows
In a preferred embodiment, suitable material of main part includes the condensed nucleus aromatic of two or more 5 or 6 rings or the organic compound of fused-ring heteroaromatic system.
The example of preferred carbocyclic fused ring system, but be not limited to, as follows
The invention still further relates to a kind of mixture, wherein at least comprise a material of main part, the spin quantum number of its ground state is 1, and Δ (S1-T1) >=0.75eV, and a metal complex, the spin quantum number of its ground state is 2.
The invention still further relates to a composition, wherein include the aforesaid mixture of at least one, at least one organic solvent.The example of organic solvent, includes, but is not limited to, methyl alcohol, ethanol, 2-methyl cellosolve, carrene, chloroform, chlorobenzene, o-dichlorohenzene, oxolane, methyl phenyl ethers anisole, morpholine, toluene, ortho-xylene, meta-xylene, paraxylene, Isosorbide-5-Nitrae dioxane, acetone, methyl ethyl ketone, 1,2 dichloroethanes, 3-phenoxytoluene, 1,1,1-trichloroethanes, 1,1,2,2-tetrachloroethanes, ethyl acetate, butyl acetate, dimethyl formamide, dimethylacetylamide, 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 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 device, 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 inkjet printing, typographic printing, silk screen printing, dip-coating, rotary coating, scraper for coating, roller printing, torsion roller printing, lithographic printing, flexographic printing, rotary printing, spraying, brushes or bat printing, slit-type squash 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, dispersant, water-repelling agent, bonding agent etc. in addition, and for adjusting viscosity, filming performance, improves tack etc.Relevant printing technique, and to the related request about solution, as solvent and concentration, viscosity etc., details refer to HelmutKipphan chief editor " print media handbook: technology and production method " (HandbookofPrintMedia:TechnologiesandProductionMethods), ISBN3-540-67326-1.
The invention further relates to an electronic device, include one or more layers organic functional thin film, wherein have at least thin film to include according to mixture of the present invention.Suitable electronic device comprises but is 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 (OrganicPlasmonEmittingDiode).Preferred organic electronic device has Organic Light Emitting Diode, organic light emission battery.
It is large-area electroluminescent device and preparation method thereof that another aspect of the present invention is to provide one, particularly include and prepare from solution, the particularly step of printing process, that is in this electroluminescent device, have at least one deck to be prepare from solution, particularly prepared by printing process.Because in large-scale production, even if only have one deck to be prepared by printing process, also greatly production cost can be reduced.In an advantageous embodiments of the present invention, luminescent layer prepares from solution, particularly prepared by printing process.Below will make some to the method preparing a functional membrane, particularly luminescent layer from solution and describe (but being not limited to).
For the ease of preparation from solution or printing, each component in luminescent layer, as matrix and/or organic free radical compound and luminous element, must be formulated in certain solvent with certain form.Said formulation forms can be solution or suspension.
In a preferential embodiment, each component in luminescent layer, can be present in an organic solvent with the form of solution or unit for uniform suspension.In certain embodiments, host material includes inorganic semiconductor nanocrystal.In some sense, this solution or unit for uniform suspension are also referred to as ultra-fine colloidal dispersion (dispersionofcolloidalpowder).Nanocrystal matrix is prepared by various method, the preparation method of semiconductor nanocrystal as previously discussed.Under certain conditions, the nanocrystal as matrix can commercially, as such as EvonikDegussa tiO 2p25.In another embodiment, material includes organic material, and it dissolves in an organic solvent.
Therefore, make this first preferential method for the functional membrane, particularly luminescent layer of device invented and include following steps:
1) various component is formulated in an organic solvent forms a solution or a unit for uniform suspension;
2) this solution or suspension are uniformly coated on substrate by printing or other coating processes;
3) toast under temperature T1, remove remaining organic solvent, and form film; This process can in atmosphere, or in inert gas, or carry out in the vacuum of appropriateness
Step 2)-3) can in atmosphere, or as carried out in glove box in inert gas.If desired, step 3) can carry out in the vacuum of appropriateness.Suitable, T1<=300 DEG C, is better <=250 DEG C, is more preferably <=220 °, preferably <=200 DEG C.This is because when large-scale production, temperature is lower, cost is also lower.Particularly, when substrate is plastics, be better T1<=250 DEG C.
In above-described device, 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 flexible.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 thin polymer film or plastics, and its vitrification point 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 polyethylene glycol (2,6-naphthalene) (PEN).
Anode can comprise a metal or conducting metal oxide, or conducting polymer.Anode can easily injected hole in HIL or HTL or luminescent layer.In the embodiment of, luminous element 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, is better be less than 0.3eV, is 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, luminous element 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, is better be less than 0.3eV, is 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, the method preparation of male or female by printing.In the embodiment of, can utilize and prepare male or female as precursor with sol-gal process containing slaine or metal complex.WO2008151094 discloses the preparations and applicatio of the ink containing slaine, and WO2010011974 discloses a kind of ink containing aluminum metal salt.Full content in the patent documentation hereby listed also will be incorporated to herein as a reference.In another embodiment, male or female makes by the ink printed containing metal nanoparticle.Some metal nano ink can commercially, as the nanometer silver paste of Xerox company and AdvancedNanoProductsCo., Ltd..
The invention still further relates to according to the application of luminescent device of the present invention in various occasion, include, but not limited to various display device, backlight, lighting source etc.
Some more detailed descriptions (but being not limited thereto) are done to organic functional material below.In WO2010135519A1, US20090134784A1 and WO2011110277A1, various organic functional material is described later in detail, hereby the full content in this 2 patent document is incorporated to herein as a reference.Organic functional material can be Small molecular and high polymer material.
1.HIM/HTM/EBM
The suitable optional compound including following construction unit of organic HIM/HTM material: phthalocyanine, porphyrin, amine, aromatic amine, biphenyl class triaryl amine, thiophene, bithiophene as two thienothiophenes and bithiophene, pyrroles, aniline, carbazole, indolocarbazole, and their derivative.The suitable HIM of another position also comprises the polymer containing fluorohydrocarbon; Polymer containing conductiving doping; Conducting polymer, 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 or EBM 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 dibenzothiophenes, dibenzofurans, furans, thiophene, benzofuran, benzothiophene, carbazole, pyrazoles, imidazoles, triazole, isoxazole, thiazole, oxadiazoles, oxatriazole, dioxazole, thiadiazoles, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazines, oxathiazine, oxadiazine, indoles, benzimidazole, indazole, indoxazine, benzoxazoles, benzisoxazole, benzothiazole, quinoline, isoquinolin, cinnoline, quinazoline, quinoxaline, naphthalene, phthalein, pteridine, xanthene, acridine, azophenlyene, phenthazine, phenoxazine, 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 oxygen atom, nitrogen-atoms, sulphur atom, silicon atom, phosphorus atoms, 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, 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 0aryl 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 atomic weight 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/HBM
The example of EIM/ETM material is not particularly limited, and any metal complex or organic compound all may be used as EIM/ETM, as long as they can transmission electronic.Preferential organic EIM/ETM material can be selected from three (oxine) aluminium (AlQ 3), azophenlyene, phenanthroline, anthracene, luxuriant and rich with fragrance, fluorenes, two fluorenes, spiral shell two fluorenes, to phenylacetylene, triazine, triazole, imidazoles, pyrene, perylene, anti-indenofluorene, along indeno, dibenzo-indenofluorene, indeno naphthalene, benzanthracene and their derivative.
Hole blocking layer (HBL) is commonly used to stop from successive functional layers, the particularly hole of luminescent layer.Contrast the luminescent device that does not have barrier layer, the existence of HBL can cause the raising of luminous efficiency usually.The hole barrier materials (HBM) of hole blocking layer (HBL) needs than successive functional layers, HOMO as lower in luminescent layer.In a preferential embodiment, HBM has the excited level larger than adjacent emissive layers, as singlet state or triplet, depends on luminous element. and in the embodiment that another is preferential, HBM has electric transmission function..The EIM/ETM material usually with dark HOMO energy level can as HBM.
On the other hand, the compound that can be used as EIM/ETM/HBM is the molecule at least comprising less than one group:
R 1optional in following group: hydrogen, alkyl, alkoxyl, 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 2meaning is identical;
Ar 1-Ar 5with the Ar described in HTM 1meaning is identical;
N be one from 0 to 20 integer;
X 1-X 8select in CH or 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.
The example of suitable done ETM compound is listed in table below:
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 alkali 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 hexatomic ring with metal M, its Atom also can by one or more R 1replace, M is alkali 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 aggregation, such as, and two alkali metal ions and two parts, 4 alkali metal ions and 4 parts, 6 alkali metal ions and 6 parts or the form at other.
The organic alkali metal compound of prioritizing selection is the compound of following chemical formula:
The symbol wherein used has above-mentioned definition identical, in addition:
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, alkali 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 host material (TripletHost):
The example of triplet host 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 luminous element, particularly triplet emitters or phosphorescent emitter 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; (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 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 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 dibenzothiophenes, dibenzofurans, dibenzoselenophene, furans, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazoles, imidazoles, triazole type, oxazole, thiazole, oxadiazoles, 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, 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 oxygen atom, nitrogen-atoms, sulphur atom, silicon atom, phosphorus atoms, 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, amino, alkene, alkynes, aralkyl, assorted alkyl, aryl and heteroaryl.
In a preferential embodiment, triplet host 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, amino, alkene, alkynes, aralkyl, assorted alkyl, aryl and heteroaryl, when they be aryl or heteroaryl time, they and above-mentioned Ar 1and Ar 2meaning is identical; N be one from 0 to 20 integer; X 1-X 8select in CH or N; X 9select in CR 1r 2or NR 1.
The example of suitable triplet host material is listed in table below:
4. singlet state host material (SingletHost):
The example of singlet state host material is not particularly limited, and any organic compound all may be used as matrix, as long as its singlet energy is than luminous element, particularly singlet emitters or fluorescent illuminant higher.
Example as the organic compound of singlet state host 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 dibenzothiophenes, dibenzofurans, dibenzoselenophene, furans, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, Pyrrolodipyridine, pyrazoles, imidazoles, triazole, isoxazole, thiazole, oxadiazoles, oxatriazole, dioxazole, thiadiazoles, pyridine, pyridazine, pyrimidine, pyrazine, triazine, 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, 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 oxygen atom, nitrogen-atoms, sulphur atom, silicon atom, phosphorus atoms, boron atom, chain structure unit and aliphatic cyclic group.。
In a preferential embodiment, singlet state host material is optional in the compound comprising at least one following group:
The example of suitable singlet state host material is listed in table below:
5. singlet emitters (SingletEmitter)
Singlet emitters often has longer conjugated pi electron system.So far, existing many examples, such as styrylamine and derivative thereof disclosed in JP2913116B and WO2001021729A1, and disclosed in WO2008/006449 and WO2007/140847 indenofluorene and derivative thereof.
In a preferential embodiment, singlet emitters can be selected from unitary styrene, binary styrylamine, ternary styrylamine, quaternary styrylamine, styrene phosphine, styrene ether and arylamine.
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 styrene is talan, and it may be substituted further.Corresponding phosphine class is similar to amine with the definition of ethers.Arylamine or aromatic amine refer to a kind of compound, the aromatic rings 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 arylamine group (diarylamino) is directly linked on anthracene, preferably on the position of 9.A fragrant anthradiamine refers to a compound, and wherein two binary arylamine 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 arylamine group is preferably linked to 1 or 1 of pyrene, on 6 positions.
Based on the example of the singlet emitters of vinylamine 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 and benzo indenofluorene-diamines, disclosed in WO2008/006449, dibenzo indenofluorene-amine and dibenzo indenofluorene-diamines, 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), naphthalene, four benzene, xanthene, luxuriant and rich with fragrance, pyrene is as 2, 5, 8, 11-tetra-t-butylperylene, indeno pyrene, penylene is as (4, 4 '-(bis (9-ethyl-3-carbazovinylene)-1, 1 '-biphenyl), periflanthene, decacyclene coronene, fluorenes, spiral shell two fluorenes, aryl pyrene (as US20060222886), arylene ethene is (as US5121029, US5130603), cyclopentadiene is as tetraphenyl cyclopentadiene, rubrene, cumarin, rhodamine, quinacridone, pyrans is as 4 (dicyanoethylene)-6-(4-dimethylaminostyryl-2-methyl)-4H-pyrane (DCM), thiapyran, bis (azinyl) imine-boron compound (US2007/0092753A1), bis (azinyl) methene compound, carbostyryl compound, oxazinone, benzoxazoles, benzothiazole, 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.
The example of some suitable singlet emitters is listed in table below:
6. triplet emitters (TripletEmitter)
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 a metallic atom, can be identical or different when L occurs at every turn, it is an organic ligand, it is connected on metallic atom 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 polymer, preferably by organic ligand by one or more position.
In a preferential embodiment, metallic atom M selects in transition metal or lanthanide series or actinides, 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 cheland, 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 multidentate ligands.Cheland 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 phenylchinolines (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 lanthanide series or actinides;
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 electrons, 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 cheland; 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, Thompsonetal.Nature403, (2000), 750-753, US20090061681A1, US20090061681A1, Adachietal.Appl.Phys.Lett.78 (2001), 1622-1624, J.Kidoetal.Appl.Phys.Lett.65 (1994), 2124, Kidoetal.Chem.Lett.657, 1990, US2007/0252517A1, Johnsonetal., JACS105, 1983, 1795, Wrighton, JACS96, 1974, 998, Maetal., 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.
7. high polymer
High polymer, i.e. Polymer, comprise homopolymers (homopolymer), copolymer (copolymer), block copolymer (blockcopolymer). in addition in the present invention, high polymer also comprises tree (dendrimer). about the synthesis of tree and application refer to DendrimersandDendrons, Wiley-VCHVerlagGmbH & Co.KGaA, 2002, Ed.GeorgeR.Newkome, CharlesN.Moorefield, FritzVogtle.
Conjugated highpolymer (conjugatedpolymer) is that its main chain backbone of a high polymer mainly makes to be made up of the sp2 hybridized orbit of C atom, and famous example has polyacetylene polyacetylene and poly (phenylenevinylene); Also can being replaced by other non-C atoms of C atom on its main chain, and when the sp2 hydridization on main chain is interrupted by some natural defects, still by people for being conjugated highpolymer. conjugated highpolymer also comprises on main chain and includes arylamine (arylamine) in the present invention in addition, aryl hydrogen phosphide (arylphosphine), and other heterocyclic arenes (heteroarmotics), metal-organic complex (organometalliccomplexes) etc.
In a preferential embodiment, being suitable for high polymer of the present invention is conjugated highpolymer.Usually, conjugated highpolymer has following general formula:
Wherein B, A can independently select identical or different construction unit when repeatedly occurring
B: the pi-conjugated construction unit with larger energy gap, also claims key unit (BackboneUnit), and be selected from monocycle or polyaromatic or heteroaryl, the unit form of prioritizing selection is benzene, diphenylene (Biphenylene), naphthalene, anthracene, phenanthrene, dihydro is luxuriant and rich with fragrance, and 9,10-dihydro is luxuriant and rich with fragrance, fluorenes, two fluorenes, spiral shell two fluorenes, to phenylacetylene, anti-indenofluorene, along indeno, dibenzo-indenofluorene, indeno naphthalene and their derivative.
A: the pi-conjugated construction unit with less energy gap, also functional unit (FunctionalUnit) is claimed, according to different functional requirements, optional self-contained have above-described hole inject or transferring material (HIM/HTM), hole barrier materials (HBM), electron injection or transferring material (EIM/ETM), electron-blocking materials (EBM), organic host materials (Host), singlet emitters (fluorescent illuminant), the construction unit of heavy state luminous element (phosphorescent emitter).
X, y:>0, and x+y=1;
In a preferential embodiment, high polymer HTM material is homopolymers, and preferential homopolymers is selected from polythiophene, polypyrrole, polyaniline, poly-biphenyl class triaryl amine, Polyvinyl carbazole and their derivative.
In the embodiment that another is preferential, high polymer HTM material is the conjugated copolymer that chemical formula 1 represents, wherein
A: the function base with hole transport capability, the optional self-contained construction unit having the injection of above-described hole or transferring material (HIM/HTM); In a preferential embodiment, A is selected from amine, biphenyl class triaryl amine, thiophene, bithiophene as two thienothiophenes and bithiophene, pyrroles, aniline, carbazole, indenocarbazole, indolocarbazole, pentacene, phthalocyanine, porphyrin and their derivative.
X, y:>0, and x+y=1; Usual y >=0.10, relatively good is >=0.15, and more preferably >=0.20, is preferably x=y=0.5.
List the suitable example that can be used as the conjugated highpolymer of HTM below:
Wherein
R is hydrogen separately independently of one another, there is the straight chained alkyl of 1 to 20 C atom, alkoxyl or thio alkoxy group, or there is the alkyl of the side chain of 3 to 20 C atoms or ring-type, alkoxyl or thio alkoxy group or silyl-group, or there is the keto group of replacement of 1 to 20 C atom, there is the alkoxycarbonyl groups of 2 to 20 C atoms, there is the aryloxycarbonyl group of 7 to 20 C atoms, cyano group (-CN), carbamoyl group (-C (=O) NH 2), halogen formyl group (-C (=O)-X wherein X represents halogen atom), formyl group (-C (=O)-H), isocyano group group, isocyanate groups, thiocyanates group or isothiocyanates group, oh group, nitryl group, CF3 group, Cl, Br, F, crosslinkable group or there is substituted or unsubstituted aromatics or the heteroaromatic ring system of 5 to 40 annular atomses, or there is aryloxy group or the heteroaryloxy group of 5 to 40 annular atomses, or the combination of these systems, wherein one or more radicals R can form aliphatic series or the aromatics ring system of monocycle or many rings each other and/or with the ring of described radicals R bonding,
R is 0,1,2,3 or 4;
S is 0,1,2,3,4o or 5;
X, y:>0, and x+y=1; Usual y >=0.10, relatively good is >=0.15, and more preferably >=0.20, is preferably x=y=0.5.
Organic ETM material of another kind of prioritizing selection is the high polymer with electron transport ability, comprises conjugated highpolymer and non-conjugated high polymer.
The high polymer ETM material of prioritizing selection is homopolymers, preferential homopolymers is selected from poly-luxuriant and rich with fragrance (polyphenanathrene), poly-phenanthroline (polyphenanthroline), poly-indenofluorene (poly-indenolfluorene)), poly-spiral shell two fluorenes (polyspiro-bifluorene), polyfluorene (polyfluorene) and their derivative.
The high polymer ETM material of prioritizing selection is the conjugated copolymer that chemical formula 1 represents, wherein A can independently select identical or different form when repeatedly occurring:
A: the function base with electron transport ability, is preferentially selected from three (oxine) aluminium (AlQ3), benzene, diphenylene, naphthalene, anthracene, luxuriant and rich with fragrance, Dihydrophenanthrene, fluorenes, two fluorenes, spiral shell two fluorenes, to phenylacetylene Bi ， perylene, 9,10-Dihydrophenanthrene, azophenlyene, phenanthroline, anti-indenofluorene, along indeno, dibenzo-indenofluorene, indeno naphthalene, benzanthracene and their derivative
X, y:>0, and usual y >=0.10 of x+y=1., relatively good is >=0.15, and more preferably >=0.20, is preferably x=y=0.5.
In a preferential embodiment, luminous high polymer has the conjugated highpolymer high polymer of following general formula to have following general formula:
B: identical with the definition of chemical formula 1.
A1: the function base with hole or electron transport ability, optional self-containedly have above-described hole to inject or transferring material (HIM/HTM), or the construction unit of electron injection or transferring material (EIM/ETM).
A2: the group with lighting function, optional self-containedly have above-described singlet emitters (fluorescent illuminant), the construction unit of heavy state luminous element (phosphorescent emitter).
X, y, z:>0, and x+y+z=1;
The example of luminous high polymer is open in following patent application: WO2007043495, WO2006118345, WO2006114364, WO2006062226, WO2006052457, WO2005104264, WO2005056633, WO2005033174, WO2004113412, WO2004041901, WO2003099901, WO2003051092, WO2003020790, WO2003020790, US2020040076853, US2020040002576, US2007208567, US2005962631, EP201345477, EP2001344788, DE102004020298, full content in above patent document is incorporated to herein as a reference by spy.
In another embodiment, being suitable for high polymer of the present invention is non-conjugated highpolymer.This can be all functions group all on side chain, and main chain is unconjugated high polymer.Some are used as this kind of non-conjugated high polymer of phosphorescence host or phosphorescent light-emitting materials at US7250226B2, JP2007059939A, have open in the patent applications such as JP2007211243A2 and JP2007197574A2, some this kind of non-conjugated high polymers being used as fluorescence luminescent material have open in the patent applications such as JP2005108556, JP2005285661 and JP2003338375.In addition, non-conjugated high polymer can be also a kind of high polymer, and on main chain, the functional unit of conjugation is got up by unconjugated link unit link, and the example of this high polymer has open in DE102009023154.4 and DE102009023156.0.Full content in above patent document is incorporated to herein as a reference by spy.
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. material
Llowing group of materials will by with in specific embodiment.
Main body 1 is material of main part (ALD-E00, Jilin Aurion moral Materials Technology Ltd.), and luminous element 1 is green glow phosphorescent emitter (ALD-H004, Jilin Aurion moral Materials Technology Ltd.).Luminous element 2 to be spin quantum numbers be 2 metal complex, its synthesis according to J.AM.CHEM.SOC.2010,132,14273 – 14278.TFB (poly [(9,9-dioctylfluorenyl-2,7-diyl)-co-(4,4'-(N-(4-sec-butylphenyl)) diphenylamine)], H.W.SandsCorp) be a kind of organic hole transport material, the method synthesis that it also can be known in document, as disclosed in the patent application of WO99/54385.(1,3,5-Tris (1-phenyl-1H-benzimidazol-2-yl) benzene is as electron transport material and exciton-blocking material (ALD-C003, Jilin Aurion moral Materials Technology Ltd.) for TPBi.
2. the preparation of luminescent device
Device architecture row in Table 1.Luminescent device follows these steps to preparation.
1. substrate prepares: the ITO electro-conductive glass substrate of patterning uses various solvent (chloroform → acetone → isopropyl alcohol) to clean first, then carries out UV ozone plasma treatment.
Rotary coating is at ITO electro-conductive glass substrate in atmosphere in clean room for 2.HIL:PEDOT:PSS (CleviosPVPAI4083), and obtaining thickness is 80nm.Then at 120 DEG C, unwatering in 10 minutes is toasted in atmosphere.
TFB, as hole transmission layer, is first dissolved in toluene with the concentration of 0.5wt% by 3.HTL:TFB, on PEDOT:PSS film, is then annealed 60 minutes at 180 DEG C by this solution rotary coating in nitrogen glove box.The thickness obtaining TFB is 10-20nm.
4.EML: in LED1-LED2, EML according to the component in table 1 10 -7in the vacuum atmosphere of Torr, by the method for vacuum thermal evaporation, and by use metal mask, steam deposition altogether and form.
5.ETL or ExBL: be by 10 -7in the vacuum atmosphere of Torr, by the method for vacuum thermal evaporation, and formed by use metal mask deposition.
6. negative electrode: all negative electrodes are all 10 -7in the vacuum atmosphere of Torr, by the method for vacuum thermal evaporation, and by use metal mask, deposition forms.
7. encapsulate: all devices in nitrogen glove box with the in addition glass cover-plate encapsulation of a kind of ultraviolet hardening resin.
Table 1
Device EML ETM(ExBL) Negative electrode
LED1 Main body 1:(15%) luminous element 1 (40nm) TPBi(20nm) LiF(1nm)/Al(100nm)
LED2 Main body 1:(15%) luminous element 2 (40nm) TPBi(20nm) LiF(1nm)/Al(100nm)
3. photophore measurement and compare
Current/voltage (I-V) characteristic of LED carrys out record by computer-controlled (Keithley2400sourcemeasurementunit) and (Keithley2000multimeter), simultaneously, brightness is measured by using the silicon photoelectric diode (Newport2112) calibrated.Electroluminescent spectrum is measured by spectrometer (OceanOpticsUSB2000).The performance of LED1-2 is summarised in table 2 below, and wherein EQE (ExternalQuantumEfficiency) represents external quantum efficiency.In LED1, the T1 of main body 1 is very low, by whole for the triplet excitons of luminous element 1 cancellation.Even if the T1 of main body 1 is very low in LED2, luminous element 2 so has higher luminous efficiency, and this may be 2 with the ground state spin quantum number of luminous element 2, thus its excitation state can not by main body 1 cancellation.
Table 2
Device Ignition voltage (V) Maximum EQE (%)
LED1 >10 0.0％
LED2 3.10 8.4％

Claims (10)

1. an electroluminescent device, comprises 1) luminescent layer, wherein at least comprise a material of main part, the spin quantum number of its ground state is 1, and Δ (S1-T1) >=0.75eV, and a metal complex, the spin quantum number of its ground state is 2; 2) positive electrode of functional layer side is arranged in; 3) negative electrode of functional layer opposite side is arranged in.
2. electroluminescent device according to claim 1, wherein metal complex includes Au, Ag, Cu.
3., according to electroluminescent device any one in claim 1-2, wherein material of main part is the group comprising following chemical formula:
Wherein
A,B 1, B 2independent of each otherly when multiple appearance be selected from a divalent group, be preferable over-CR 1r 2-,-NR 1-,-PR 1-,-O-,-S-,-SO-,-SO 2-,-CO-,-CS-,-CSe-,-P (=O) R 1-,-P (=S) R 1-,-SiR 1r 2-,-CR 1r 2-CR 3r 4-,-CR 1r 2-SiR 3r 4,-CR 1r 2-NR 3-,-CR 1r 2-O-,-CR 1r 2-NR 3-,-CR 1r 2-C (=O)-,-CR 1r 2-S-,-SiR 1r 2-NR 3-,-SiR 1r 2-O-,-SiR 1r 2-NR 3-,-SiR 1r 2-C (=O)-,-SiR 1r 2-S-,-CR 1=CR 1-,-CR 1=N-,-CR 1=CR 1-,-C ≡ C-,
R 1, R 2, R 1, R 2be identical or different group independent of each other, can select in H, halogen ,-CN ,-NC ,-NCO ,-NCS ,-OCN ,-SCN ,-C (=O) NR 0r 00,-C (=O) R 0,-NH 2,-NR 0r 00,-SH ,-SR 0,-SO 3h ,-SO 2r 0,-OH ,-NO 2,-CF 3,-SF 5, the optional silicyl replaced, or include alkyl or the carbonyl of 1 to 40 carbon atom, they can be optionally substituted, and optionally comprise one or more hetero-atom,
R 0, R 00be alkyl or the carbonyl of hydrogen independent of each other or optional replacement, optionally comprise one or more hetero-atom group,
Every n is independently 0 or 1, is 0 or 1 with corresponding each h at same subunit,
M is >=integer of 1.
4., according to electroluminescent device any one in claim 1-2, wherein material of main part is the organic compound including condensed nucleus aromatic or fused-ring heteroaromatic system.
5., according to electroluminescent device any one in claim 1-3, wherein material of main part includes following carbocyclic fused ring system
6. a mixture, wherein at least comprises a material of main part, and the spin quantum number of its ground state is 1, and Δ (S1-T1) >=0.75eV, and a metal complex, the spin quantum number of its ground state is 2.
7. a composition, wherein at least comprises a mixture according to claim 6, and at least one organic solvent.
8. the application of mixture according to claim 6 in organic electronic device.
9. an organic electronic device, wherein at least comprises a mixture according to claim 6.
10. organic electronic device 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 (OrganicPlasmonEmittingDiode).
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