CN110494514A - The preparation of organic functional material - Google Patents

The preparation of organic functional material Download PDF

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Publication number
CN110494514A
CN110494514A CN201880023992.6A CN201880023992A CN110494514A CN 110494514 A CN110494514 A CN 110494514A CN 201880023992 A CN201880023992 A CN 201880023992A CN 110494514 A CN110494514 A CN 110494514A
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group
carbon atoms
organic
solvent
preparation
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Inventor
李·坦
帕维尔·麦斯凯万茨
菲利普·梅
丹尼尔·瓦尔克
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Merck Patent GmbH
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Merck Patent GmbH
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/36—Inkjet printing inks based on non-aqueous solvents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/50—Sympathetic, colour changing or similar inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/52—Electrically conductive inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H10K71/13—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H10K71/13—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing
    • H10K71/135—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing using ink-jet printing
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H10K71/15—Deposition of organic active material using liquid deposition, e.g. spin coating characterised by the solvent used
    • 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 relates to the preparations for containing at least one organic functional material and at least the first organic solvent, wherein first organic solvent contains at least one carbonate group, and the electronic device prepared by using these preparations.

Description

The preparation of organic functional material
Technical field
The present invention relates to the preparations for containing at least one organic functional material and at least the first organic solvent, wherein described the One organic solvent contains at least one carbonate group, and the electroluminescent device prepared by using these preparations.
Background technique
Organic luminescent device (OLED) is manufactured by vacuum deposition process for a long time.It has sufficiently had studied recently such as Other technologies of ink jet printing, because they have the advantages that such as to save cost and popularization possibility.Multi-sheet printed Significant challenge first is that determining relevant parameter to obtain uniform ink deposition in substrate.In order to trigger these parameters, such as Some additives can be added in surface tension, viscosity or boiling point into preparation.
Summary of the invention
Technical problem and goal of the invention
Many solvents have been proposed in the organic electronic device for ink jet printing.However, in deposition and back tender The quantity of the important parameter to work in skill makes the selection of solvent very challenging.Therefore, containing for passing through ink-jet It prints the organic semi-conductor preparation deposited and still needs improvement.It organic is partly led it is an object of the present invention to provide a kind of The preparation of body makes controlled deposition to form the organic semiconductor layer with good layer characteristic and efficiency performance.Of the invention Another purpose is to provide a kind of organic semi-conductor preparation, when for example in ink jet printing method in use, the preparation makes The uniformly applied ink drop in substrate is obtained, to provide good layer characteristic and efficiency performance.
Solution to the problem
The present invention is solved by providing the preparation comprising at least one organic functional material and at least the first organic solvent Above-mentioned purpose, wherein first organic solvent contains at least one carbonate group, preferably a carbonate group.
Advantageous effect of the invention
Inventor is it has surprisingly found that use the organic solvent for containing at least one carbonate group to make as the first solvent Surface tension must be fully controlled and effective ink is induced to deposit, so that it is organic to form uniform and clear and legible functional material Layer, with good layer characteristic and performance.
Detailed description of the invention
Fig. 1 shows the exemplary layer structure of device, and it includes substrate, ito anode, hole injection layers (HIL), hole transmission layer (HTL), green light emitting layer (G-EML), hole blocking layer (HBL), electron transfer layer (ETL) and Al cathode.
Specific embodiment
The present invention relates to the preparations for containing at least one organic functional material and at least the first organic solvent, wherein described the One organic solvent contains at least one carbonate group, preferably a carbonate group.
Preferred embodiment
In one preferred embodiment, the first organic solvent containing a carbonate group is according to logical formula (I) Carbonate-containing group solvent
Wherein
R1And R2It is identical or different at each occurrence, and be the alkyl or alcoxyl of the straight chain with 1 to 20 carbon atom Base group or branch or cricoid alkyl or alkoxy base with 3 to 20 carbon atoms are straight with 2 to 20 carbon atoms The alkenyl or alkenyloxy group group of chain or branch or cricoid alkenyl or alkenyloxy group group with 3 to 20 carbon atoms, or have 2 Alkynyl or alkynyloxy moieties to the straight chain of 20 carbon atoms or the branch with 3 to 20 carbon atoms or cricoid alkynyl or alkynes Oxygroup group, wherein one or more non-adjacent CH2Group can be by-O- ,-S- ,-NR3-、-CONR3,-CO-O- ,-C= O- ,-CH=CH- or-C ≡ C- are replaced, and wherein one or more hydrogen atoms can be replaced by F, or have 4 to 14 carbon atoms Aryl or heteroaryl group, or condensed heterocycle or aryl can be formed and can be by one or more non-aromatic R3Group Replace, and multiple substituent Rs on same ring or on two different rings3It can be formed together monocycle or polycyclic aliphatic series again Or aromatics ring system, the ring system can be by multiple substituent Rs3Replace；And
R3It is identical or different in each case, and be the alkyl or alkoxy of the straight chain with 1 to 20 carbon atom Group, or the branch with 3 to 20 carbon atoms or cricoid alkyl or alkoxy base, wherein one or more are non-adjacent CH2Group can be replaced by-O- ,-S- ,-CO-O- ,-C=O- ,-CH=CH- or-C ≡ C-, and wherein one or more hydrogen are former Son can be replaced by F, or have 4 to 14 carbon atoms and can be by one or more non-aromatic R3The aryl or heteroaryl that group replaces Base group.
In first preferred embodiment, the first organic solvent containing a carbonate group is according to general formula (I) solvent of carbonate-containing group, wherein
R1And R2It is identical or different at each occurrence, and be aryl or heteroaryl base with 4 to 14 carbon atoms Group, or condensed heterocycle or aryl can be formed and can be by one or more non-aromatic R3Group replaces, and same Multiple substituent Rs on ring or on two different rings3It can be formed together monocycle or polycyclic aliphatic series or aromatics ring system again, it is described Ring system can be by multiple substituent Rs3Replace.
In first most preferred embodiment, the first organic solvent containing a carbonate group is according to general formula (II) solvent of carbonate-containing group
Wherein
R3It is identical or different in each case, and be the alkyl or alkoxy of the straight chain with 1 to 20 carbon atom Group, or the branch with 3 to 20 carbon atoms or cricoid alkyl or alkoxy base, wherein one or more are non-adjacent CH2Group can be replaced by-O- ,-S- ,-CO-O- ,-C=O- ,-CH=CH- or-C ≡ C-, and wherein one or more hydrogen are former Son can be replaced by F；And
The integer that n is 0 to 5, preferably 0 to 2 and more preferable 0 or 1.
In second preferred embodiment, the first organic solvent containing a carbonate group is according to general formula (I) solvent of carbonate-containing group, wherein
R1It is the alkyl or alkoxy base or the branch with 3 to 20 carbon atoms of the straight chain with 1 to 20 carbon atom Chain or cricoid alkyl or alkoxy base, the alkenyl or alkenyloxy group group of the straight chain with 2 to 20 carbon atoms or have 3 to The branch or cricoid alkenyl or alkenyloxy group group of 20 carbon atoms, or the alkynyl or alkynes of the straight chain with 2 to 20 carbon atoms Oxygroup group or branch or cricoid alkynyl or alkynyloxy moieties with 3 to 20 carbon atoms, wherein one or more non-phases Adjacent CH2Group can be by-O- ,-S- ,-NR3-、-CONR3,-CO-O- ,-C=O- ,-CH=CH- or-C ≡ C- replace, and its Middle one or more hydrogen atom can be replaced by F；And
R2It is the aryl or heteroaryl group with 4 to 14 carbon atoms, or condensed heterocycle or aryl can be formed And it can be by one or more non-aromatic R3Group replaces, and multiple substituent groups on same ring or on two different rings R3It can be formed together monocycle or polycyclic aliphatic series or aromatics ring system again, the ring system can be by multiple substituent Rs3Replace.
In second most preferred embodiment, the first organic solvent containing a carbonate group is according to general formula (III) solvent of carbonate-containing group
Wherein
R1It is the alkyl or alkoxy base or the branch with 3 to 20 carbon atoms of the straight chain with 1 to 20 carbon atom Chain or cricoid alkyl or alkoxy base, the alkenyl or alkenyloxy group group of the straight chain with 2 to 20 carbon atoms or have 3 to The branch or cricoid alkenyl or alkenyloxy group group of 20 carbon atoms, or the alkynyl or alkynes of the straight chain with 2 to 20 carbon atoms Oxygroup group or branch or cricoid alkynyl or alkynyloxy moieties with 3 to 20 carbon atoms, wherein one or more non-phases Adjacent CH2Group can be by-O- ,-S- ,-NR3-、-CONR3,-CO-O- ,-C=O- ,-CH=CH- or-C ≡ C- replace, and its Middle one or more hydrogen atom can be replaced by F；
R3It is identical or different in each case, and be the alkyl or alkoxy of the straight chain with 1 to 20 carbon atom Group, or the branch with 3 to 20 carbon atoms or cricoid alkyl or alkoxy base, wherein one or more are non-adjacent CH2Group can be replaced by-O- ,-S- ,-CO-O- ,-C=O- ,-CH=CH- or-C ≡ C-, and wherein one or more hydrogen are former Son can be replaced by F；And
The integer that n is 0 to 5, preferably 0 to 2 and more preferable 0 or 1.
In the preferred embodiment of third, the first organic solvent containing a carbonate group is according to general formula (I) solvent of carbonate-containing group, wherein
R1And R2It is identical or different at each occurrence, and be the alkyl or alcoxyl of the straight chain with 1 to 20 carbon atom Base group or branch or cricoid alkyl or alkoxy base with 3 to 20 carbon atoms are straight with 2 to 20 carbon atoms The alkenyl or alkenyloxy group group of chain or branch or cricoid alkenyl or alkenyloxy group group with 3 to 20 carbon atoms, or have 2 Alkynyl or alkynyloxy moieties to the straight chain of 20 carbon atoms or the branch with 3 to 20 carbon atoms or cricoid alkynyl or alkynes Oxygroup group, wherein one or more non-adjacent CH2Group can be by-O- ,-S- ,-NR3-、-CONR3,-CO-O- ,-C= O- ,-CH=CH- or-C ≡ C- are replaced, and wherein one or more hydrogen atoms can be replaced by F.
In the most preferred embodiment of third, the first organic solvent containing a carbonate group is according to general formula (I) solvent of carbonate-containing group, wherein
R1And R2It is identical or different at each occurrence, and be the alkyl or alcoxyl of the straight chain with 1 to 20 carbon atom Base group, or the branch with 3 to 20 carbon atoms or cricoid alkyl or alkoxy base.
In the 4th preferred embodiment, the first organic solvent containing a carbonate group is according to general formula (I) solvent of carbonate-containing group, wherein
R1It is the alkyl or alkoxy base or the branch with 3 to 20 carbon atoms of the straight chain with 1 to 20 carbon atom The alkyl or alkoxy base of chain, the alkenyl or alkenyloxy group group of the straight chain with 2 to 20 carbon atoms or have 3 to 20 carbon The alkenyl or alkenyloxy group group of the branch of atom, or the alkynyl or alkynyloxy moieties or tool of the straight chain with 2 to 20 carbon atoms There are the alkynyl or alkynyloxy moieties of the branch of 3 to 20 carbon atoms, wherein one or more non-adjacent CH2Group can by- O-、-S-、-NR3-、-CONR3,-CO-O- ,-C=O- ,-CH=CH- or-C ≡ C- replace, and wherein one or more hydrogen are former Son can be replaced by F；And
R2It is cyclic alkyl or alkoxy base with 3 to 20 carbon atoms, there is the cricoid of 3 to 20 carbon atoms Alkenyl or alkenyloxy group group, or cricoid alkynyl or alkynyloxy moieties with 3 to 20 carbon atoms, wherein one or more are non- Adjacent CH2Group can be by-O- ,-S- ,-NR3-、-CONR3,-CO-O- ,-C=O- ,-CH=CH- or-C ≡ C- replace, and Wherein one or more hydrogen atoms can be replaced by F.
In the 4th most preferred embodiment, the first organic solvent containing a carbonate group is according to general formula (IV) solvent of carbonate-containing group,
Wherein
R1It is the alkyl group of the straight chain with 1 to 20 carbon atom or the alkyl of the branch with 3 to 20 carbon atoms Group, the alkenyl group of the alkenyl group of the straight chain with 2 to 20 carbon atoms or the branch with 3 to 20 carbon atoms, or The alkynyl group of the alkynyl group of straight chain with 2 to 20 carbon atoms or the branch with 3 to 20 carbon atoms；
R3It is identical or different in each case, and be the alkyl or alkoxy of the straight chain with 1 to 20 carbon atom Group, or the branch with 3 to 20 carbon atoms or cricoid alkyl or alkoxy base, wherein one or more are non-adjacent CH2Group can be replaced by-O- ,-S- ,-CO-O- ,-C=O- ,-CH=CH- or-C ≡ C-, and wherein one or more hydrogen are former Son can be replaced by F；And
The integer that n is 0 to 5, preferably 0 to 2 and more preferable 0 or 1.
The example and its boiling point (BP) of the solvent of preferred carbonate-containing group are shown in the following table 1.
Table 1: the solvent and its boiling point (BP) of preferred carbonate-containing group.
Preferably, surface tension >=20mN/m of the first solvent.It is highly preferred that the surface tension of the first solvent is in 25- In the range of 40mN/m and most preferably in the range of 28-37.5mN/m.
Based on the total amount of solvent in preparation, the content of the first solvent is preferably in the range of 50-100 volume %, more preferably In the range of 75-99 volume % and most preferably in the range of 90-99 volume %.
Therefore, the total amount based on solvent in preparation, the content of the second solvent are more excellent preferably in the range of 0-50 volume % It is selected in the range of 1-25 volume % and most preferably in the range of 1-10 volume %.
Preferably, the boiling point of the first solvent is in the range of 100-400 DEG C, more preferably in the range of 200-400 DEG C.
Preparation according to the present invention includes at least one to be different from the second of the first solvent in a preferred embodiment Solvent.Second solvent is used together with the first solvent.
In one embodiment, the second solvent can be the solvent of carbonate-containing group, be different from the first solvent.So And, it is preferable that the second solvent is free of carbonate group.
Suitable second solvent is preferably organic solvent, especially includes alcohol, aldehyde, ketone, ether, ester, amide such as two-C1-2Alkane Base formamide, sulphur compound, nitro compound, hydrocarbon, halogenated hydrocarbons (such as chlorinated hydrocabon), aromatics or heteroaromatic hydrocarbon and halogenated aromatic Or heteroaromatic hydrocarbon.
Preferably, the second solvent can be selected from following one: replace and non-substituted aromatics or linear ester, such as benzoic acid Ethyl ester, butyl benzoate；Replace and non-substituted aromatics or linear, such as 3- phenoxytoluene or methyl phenyl ethers anisole；Replace or non- Substituted arene derivatives, such as dimethylbenzene；Indan derivative, such as hexamethyl indane；Substitution and non-substituted aromatics are straight Chain ketone；Replace and non-substituted heterocycle, such as pyrrolidones, pyridine, pyrazine；Other fluorinations or chlorinating aromatic hydrocarbon.
Particularly preferred second organic solvent is such as 1,2,3,4- durols, 1,2,3,5- durol, 1,2,3- Trimethylbenzene, 1,2,4,5- durol, 1,2,4- trichloro-benzenes, 1,2,4- trimethylbenzene, 1,2- dihydronaphthalene, 1,2- dimethyl Naphthalene, 1,3- benzo dioxolane, 1,3- diisopropyl benzene, 1,3- dimethylnaphthalene, Isosorbide-5-Nitrae-benzo twoAlkane, Isosorbide-5-Nitrae-diisopropyl Base benzene, Isosorbide-5-Nitrae-dimethylnaphthalene, 1,5- dimethyl tetrahydronaphthalene, 1- benzothiophene, sulphur naphthalene, 1- bromonaphthalene, 1 chloromethyl naphthalene, 1- ethyl Naphthalene, 1- methoxynaphthalene, 1- methyl naphthalene, 1- methyl indol, 2,3- benzofurans, 2,3- Dihydrobenzofuranes, 2,3- dimethyl benzenes Methyl ether, 2,4- dimethylanisoles, 2,5- dimethylanisoles, 2,6- dimethylanisoles, 2,6- dimethylnaphthalenes, the bromo- 3- of 2- Bromomethyl naphthalene, 2- bromomethyl naphthalene, 2- bromonaphthalene, 2- ethyoxyl naphthalene, 2-ethylnaphthalene, 2- cumene methyl ether, 2- methylanisole, 2- Methyl indol, 3,4- dimethylanisoles, 3,5- dimethylanisoles, 3- bromoquinoline, 3- methylanisole, 4- methylbenzene first Ether, 5- decalactone, 5- methoxyindan, 5- methoxy-Indole, 5- tert-butyl meta-xylene, 6- methylquinoline, 8- methylquinoline, Acetophenone, methyl phenyl ethers anisole, benzonitrile, benzothiazole, benzyl acetate, bromobenzene, butyl benzoate, butyl phenylate, cyclohexylbenzene, decahydro Naphthols, dimethoxy-p, 3- phenoxytoluene, diphenyl ether, propiophenone, ethylbenzene, ethyl benzoate, own benzene, indane, hexamethyl Indane, indenes is heterochromatic full, cumene, m-Methylisopropylbenzene, mesitylene, methyl benzoate, ortho-xylene, and meta-xylene is right Dimethylbenzene, propyl benzoate, propyl benzene, o-dichlorohenzene, penta benzene, benzyl carbinol, ethoxybenzene, phenylacetate, p-Methylisopropylbenzene, benzene Acetone, sec-butylbenzene, tert-butyl benzene, thiophene, toluene, veratryl alcohol, monochlorobenzene, o-dichlorohenzene, pyridine, pyrazine, pyrimidine, pyrrolidines The mixture of ketone, morpholine, dimethyl acetamide, dimethyl sulfoxide, decahydronaphthalenes and/or these compounds.
These solvents can be used alone or as the mixture for forming two kinds of the second solvent, three or more solvents It uses.
Preferably, the boiling point of the second solvent is in the range of 100-400 DEG C, more preferably in the range of 150-350 DEG C.
Solubility of at least one organic functional material in the first solvent and the second solvent is preferably in 1-250g/ In the range of l and more preferably in the range of 1-50g/l.
Total weight based on preparation, the content of at least one of described preparation organic functional material is in 0.001-20 weight % In the range of, preferably in the range of 0.01-10 weight %, more preferably exist in the range of 0.1-5 weight % and most preferably In the range of 0.3-5 weight %.
The surface tension of preparation according to the present invention is preferably in the range of 10-50mN/m and more preferably in 25-40mN/ In the range of m.
In addition, the viscosity of preparation according to the present invention is preferably in the range of 1-50mPa.s, more preferably in 2-40mPa.s In the range of, and most preferably in the range of 2-20mPa.s.
Preferably, the surface tension of organic solvent blend is in the range of 15-80mN/m, more preferably in 20-60mN/m In the range of and most preferably in the range of 25-40mN/m.The contact of FTA (First Ten Angstrom) 1000 can be used Angle angular instrument surface tension at 20 DEG C.The details of the method " can use liquid from Roger P.Woodward, Ph.D. Drip stalagmometry (the Surface Tension Measurements Using the Drop Shape of Method On Shape Method) " the First Ten Angstrom announced is obtained.Preferably, sessile drop method can be used to determine surface tension.The measurement Technology will be in liquid droplet distribution to the liquid of entirety or gas phase from syringe needle.The shape of drop is by surface tension, gravity and density variation Between relationship generate.Using sessile drop method, http://www.kruss.de/services/education-theory/ is used Shadow image gauging surface tension of the glossary/drop-shape-analys is from hanging drop.It is a kind of commonly and commercial Obtainable high-precision Drop Shape Analysis tool comes from First TenFTA1000, for executing There is stalagmometry.Surface tension is determined by software FTA1000.It is all to measure within the scope of 20 DEG C to 22 DEG C at room temperature It carries out.S.O.P. includes that the surface of every kind of preparation is measured using new disposable drop distribution system (syringe and syringe needle) Tension.It was measured within one minute duration with 60 times to measure each drop, these measurement results is averaged later. For every kind of preparation, three drops are measured.End value is averaged to the measurement result.It is periodically well-known for having Surface tension various liquid to the tool cross-check.
On TA instrument ARG2 rheometer, in 10-1000s-1Range of shear rate in, use 40mm parallel plate geometry knot Structure measures the viscosity of preparation and solvent according to the present invention.Measurement result is taken as 200-800s-1Average value, wherein accurate control Temperature and shear rate processed.The viscosity provided in table 3 is the at a temperature of viscosity of every kind of preparation that measures at 25 DEG C.Every kind of solvent Measurement is three times.The viscosity number is the average value taken to the measurement result.
Preparation according to the present invention includes at least one organic functional material, can be used for manufacturing the function of electronic device Layer.Functional material is usually the organic material introduced between the anode and cathode of electronic device.
Term organic functional material especially indicates organic conductor, organic semiconductor, organic fluorescent compounds, organic phosphorus photochemical Close object, organic light-absorbing compound, organic photosensitive chemical combination object, organic photosensitizer and other organic photoactive compounds.Term has Machine functional material also covers the metal-organic complex of transition metal, rare earth element, lanthanide series and actinides.
Organic functional material be selected from fluorescent illuminant, phosphorescent emitter, material of main part, host material, exciton-blocking material, Electron transport material, electron injection material, hole conductor material, hole-injecting material, n-type dopant, p-type dopant, broadband Gap material, electron-blocking materials and hole barrier materials.
The preferred embodiment of organic functional material is disclosed in detail in WO 2011/076314A1, and wherein the document is to draw During mode is incorporated herein.
In one preferred embodiment, organic functional material is selected from hole-injecting material, hole mobile material, hair The organic semiconductor of luminescent material, electron transport material and electron injection material.
It is highly preferred that organic functional material is the organic semiconductor selected from hole injection and hole mobile material.
Organic functional material can be the compound with low molecular weight, polymer, oligomer or dendritic macromole, Middle organic functional material is also possible to the form of mixture.Therefore, preparation according to the present invention may include two different having The compound of low molecular weight, a kind of compound with low molecular weight and a kind of polymer or two kinds of polymer (blend).
Organic functional material is usually described via the property for the frontal orbital being described in more detail below.The material Molecular orbit, especially up to occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO), their energy level and Minimum triplet T1Energy or lowest excited singlet state S1Energy be to be determined via quantum-Chemical Calculation.In order to calculate not There is the organic substance of metal, " ground state/semiempirical/default spin/spin of AM1/ charge 0/ singlet state " method is used to carry out first Geometrical optimization.Then the geometry based on optimization implements energy balane.Use herein " spin of TD-SCF/DFT/ default/ B3PW91 " method and " 6-31G (d) " base group (charge 0, spin singlet state).For metal-containing compound, via " ground state/ Hartree-Fock/ defaults the spin/spin of LanL2MB/ charge 0/ singlet state " method geometry optimization.Similar to above-mentioned pass It being made energy calculation in the method for organic substance, difference is to use " LanL2DZ " base group for metallic atom, and for ligand Use " 6-31G (d) " base group.Energy balane obtains the HOMO energy level HEh or lumo energy LEh measured with Hartree units.Ginseng Examine cyclic voltammetry measurement calibration the HOMO and lumo energy with electronic voltmeter thereby determine that it is as follows:
HOMO (eV)=((HEh*27.212) -0.9899)/1.1206
LUMO (eV)=((LEh*27.212) -2.0041)/1.385
For purposes of this application, these values are considered separately as the HOMO and lumo energy of material.
Minimum triplet T1It is defined as the triplet with minimum energy generated by described quantum-Chemical Calculation Energy.
Lowest excited singlet state S1It is defined as the swashing with minimum energy generated by described quantum-Chemical Calculation Send out the energy of singlet state.
Method described herein is unrelated with software package used and provides identical result always.It is common for this purpose The example of program is " Gaussian09W " (Gaussian company) and Q-Chem 4.1 (Q-Chem company).
Compound with hole-injection characteristics, referred to herein as hole-injecting material, simplify or promotion hole is Positive charge is transferred in organic layer from anode.In general, the HOMO energy level of hole-injecting material is near anode energy level or is higher than positive Pole energy level, that is, be generally at least -5.3eV.
Compound with hole transporting properties, referred to herein as hole mobile material can transmit usually from sun Pole or adjacent layer such as hole injection layer injected holes, i.e. positive charge.Hole mobile material usually have preferably at least- The high HOMO energy level of 5.4eV.Depending on the structure of electronic device, hole mobile material can also be used to inject material as hole Material.
Preferred compound with hole injection and/or hole transporting properties includes such as triarylamine, benzidine, four virtues Base-p-phenylenediamine, triaryl phosphine, phenthazine, phenoPiperazine, dihydrophenazine, thianthrene, dibenzo oneself bright-coloured ring, pheno to dioxaThiophene, Carbazole, Azulene, thiophene, pyrroles and furan derivatives and other containing with high HOMO (HOMO=highest occupied molecular orbital) O, the heterocyclic compound of S or N.
It, can specifically mentioned phenylenediamine derivative (US as the compound with hole injection and/or hole transporting properties 3615404), arylamine derivatives (US 3567450), the chalcone derivative (US 3526501) that amino replaces, styryl Anthracene derivant (JP-A-56-46234), polynuclear aromatic compound (EP 1009041), poly- aromatic yl paraffin derivative (US 3615402), fluorenone derivatives (JP-A-54-110837), hydazone derivative (US 3717462), acyl group hydrazone, stilbene derivative (JP- A-61-210363), silazane derivatives (US 4950950), polysilane (JP-A-2-204996), aniline (JP-A- 2-282263), thiophene oligomers (JP Heisei 1 (1989) 211399), polythiophene is poly- (N- vinyl carbazole) (PVK), poly- pyrrole It coughs up, polyaniline and other conductive macromoleculars, porphyrin compound (JP-A-63-2956965, US 4720432), aromatics diformazan subunit Type compound, carbazole compound, such as CDBP, CBP, mCP, aromatic uncle amine and styrylamine compound (US 4127412), example Such as the triphenylamine of benzidine-type, the triphenylamine of the triphenylamine of styrylamine type and two amine type.Arylamine dendroid can also be used Macromolecular (JP Heisei 8 (1996) 193191), monomelic triarylamines (US 3180730) contain one or more vinyl groups And/or the triarylamine (US 3567450 and US 3658520) or four aryl two of at least one functional group for containing reactive hydrogen Amine (two tertiary amine units are connected via aryl group).More triaryl amino groups also are present in molecule.Phthalein Cyanines derivative, naphthalocyanine derivative, butadiene derivatives and quinoline, such as two pyrazines simultaneously [2,3-f:2', 3'-h] quinoline Quinoline pregnancy nitrile is also suitable.
Aromatic uncle amine (2008/0102311 A1, US 4720432 of US preferably containing at least two tertiary amine units With US 5061569), for example, NPD (bis- [N- (1- the naphthalene)-N- phenyl amino] biphenyl of α-NPD=4,4'-) (US 5061569), TPD 232 (bis- (N, N'- diphenyl -4- the aminophenyl)-N of=N, N'-, N- diphenyl -4,4'- diaminostilbene, 1'- biphenyl) or MTDATA (MTDATA or m-MTDATA=4,4', 4 "-three [3- aminomethyl phenyl) phenyl amino] triphenylamine) (JP- A-4-308688), TBDB (=N, N, N', N'- tetra- (4- biphenyl) benzidine subunit), (=1,1- is bis-, and (4- bis- is to first by TAPC Phenylaminophenyl) hexamethylene), TAPPP (bis- (4- di-p-tolyl the aminophenyl) -3- phenyl-propanes of=1,1-), BDTAPVB Bis- [2- [4- [N, N- bis- (p-methylphenyl) amino] phenyl] vinyl] benzene of (=1,4-), (=N, N, N', N'- tetra- are to toluene by TTB Base -4,4'- benzidine), TPD (bis- [N-3- the aminomethyl phenyl]-N- phenyl aminos of=4,4'-) biphenyl), N, N, N', N'- tetra- 4,4 " '-diaminostilbene of phenyl-, 1', 4', 1 ", 4 ", 1 " '-quaterphenyl, the similar tertiary amine containing carbazole unit, such as TCTA Bis- [4- (9H- carbazole -9- base) phenyl] aniline of (=4- (9H- carbazole -9- base)-N, N-).It is also preferred that according to US Six azepine benzo phenanthrene compounds and phthalocyanine derivates (such as the H of 2007/0092755A12Pc, CuPc (=copper phthalocyanine), CoPc, NiPc、ZnPc、PdPc、FePc、MnPc、ClAlPc、ClGaPc、ClInPc、ClSnPc、Cl2SiPc、(HO)AlPc、(HO) GaPc、VOPc、TiOPc、MoOPc、GaPc-O-GaPc)。
The particularly preferably triarylamine compound of following formula (TA-1) to (TA-12), is disclosed in EP 1162193 B1, EP 650 955 B1, Synth.Metals (synthesis metal), 1997,91 (1-3), 209, DE 19646119 A1, WO 2006/122630 A1, EP 1 860 097 A1, EP 1834945 A1, JP 08053397 A, US 6251531 B1, US 2005/0221124, JP 08292586 A, US 7399537 B2, US 2006/0061265 A1, EP 1 661 888 and WO In 2009/041635.The compound of the formula (TA-1) to (TA-12) can also be substituted:
The other compounds that may be used as hole-injecting material are described in 0891121 A1 and EP 1029909A1 of EP, Implanted layer general description is in 2004/0174116 A1 of US.
These arylamines and heterocyclic compound for being typically used as hole injection and/or hole mobile material preferably result in polymerization HOMO in object is greater than -5.8eV (relative to vacuum level), especially preferred more than -5.5eV.
Compound with electron injection and/or electron transport property be for example pyridine, pyrimidine, pyridazine, pyrazine,Two Azoles, quinoline, quinoxaline, anthracene, benzanthracene, pyrene, benzimidazole, triazine, ketone, phosphine oxide and phenazene derivative and triaryl Borine and the other heterocyclic compound containing O, S or N with low LUMO (LUMO=lowest unoccupied molecular orbital).
Specially suitable compound for electron-transport and electron injecting layer is the metallo-chelate (example of 8-hydroxyquinoline Such as LiQ, AlQ3、GaQ3、MgQ2、ZnQ2、InQ3、ZrQ4), BAlQ, Ga class oxyquinoline complex compound, 4- aza-phenanthrenes -5- alcohol-Be network Close object (US 5529853A, referring to formula ET-1), butadiene derivatives (US 4356429), heterocyclic optical brighteners (US 4539507), benzimidizole derivatives (US 2007/0273272A1), such as TPBI (US 5766779, referring to formula ET-2), 1, 3,5- triazines, such as two fluorenyl pyrrolotriazine derivatives (such as according to DE 102008064200) of spiral shell, pyrene, anthracene, aphthacene, fluorenes, spiral shell Fluorenes, dendritic macromole, aphthacene (such as rubrene derivative), 1,10- phenanthroline derivative (JP 2003-115387, JP 2004-311184, JP-2001-267080, WO 02/043449), Silole derivative (EP 1480280, EP 1478032, EP 1469533), borane derivative, such as containing Si triarylborane derivative (2007/0087219 A1 of US, Referring to formula ET-3), pyridine derivate (JP 2004-200162), phenanthroline, especially 1,10- phenanthroline derivative, such as BCP And Bphen, and some phenanthroline (US 2007-0252517 A1) for connecting via xenyl or other aromatic groups or with The phenanthroline (US 2007-0122656 A1, referring to formula ET-4 and ET-5) of anthracene connection.
Equally suitable is heterocyclic organic compounds, for example, thiopyrandioxide,Azoles, triazole, imidazoles orDiazole. Using the pentacyclic example containing N, for example,Azoles, preferably 1,3,4-Diazole, such as formula ET-6, ET-7, ET-8 and ET-9 Compound, be especially disclosed in 2007/0273272 A1 of US；Thiazole,Diazole, thiadiazoles, triazole, referring particularly to US 2008/0102311 A1 and Y.A.Levin, M.S.Skorobogatova, Khimiya Geterotsiklicheskikh Soedinenii 1967 (2), 339-341, the preferably compound of formula ET-10, Silole derivative.Preferredization Closing object is following formula (ET-6) to (ET-10):
Organic compound, such as Fluorenone, fluorenes subunit methane, tetra-carbonic, anthraquinone bismethane, diphenylquinone, anthracene also can be used The derivative of ketone and anthraquinone diethyl subunit diamines.
The anthracene (there is 1- naphthalene or 2- naphthalene and 4- xenyl or 3- xenyl) or contain that preferably 2,9,10- replaces Molecule (the US2008/0193796A1, referring to formula ET-11) of two anthracene units.Furthermore the anthracene that very advantageously 9,10- replaces Connection (US 1551206 A1 of 2006/147747 A and EP, referring to formula ET-12 and ET- of unit and benzimidizole derivatives 13)。
The compound that electron injection and/or electron transport property can be generated preferably results in LUMO (relatively less than -2.5eV In vacuum level), particularly preferably less than -2.7eV.
Invention formulation may include illuminator.Term illuminator indicates occurring by any kind of energy transfer After excitation, so that radiation transistion is to ground state and luminous material.In general, it is known that two class illuminators, i.e. fluorescence and phosphorescence Illuminator.Term fluorescent illuminant indicates material or compound that the radiation transistion from excited singlet state to ground state wherein occurs. Term phosphorescent emitter preferably indicates luminescent material or compound containing transition metal.
If illuminator causes the above-mentioned characteristic in system, illuminator is also commonly referred to as dopant.Include host material It is considered referring to the lesser component of ratio in the mixture with the dopant in the system of dopant.It correspondingly, include matrix material Host material in the system of material and dopant is considered referring to the component of large percentage in the mixture.Therefore, term phosphorescence Illuminator, which also may be considered that, refers to such as phosphorescent dopants.
The compound that can be shone especially includes fluorescent illuminant and phosphorescent emitter.These especially include containing Stilbene, Stilbene Amine, styrylamine, cumarin, rubrene, rhodamine, thiazole, thiadiazoles, cyanine, thiophene, to benzene subunit, phthalocyanine, porphyrin, Ketone, quinoline, imines, anthracene and/or pyrene structure compound.It particularly preferably can be even at room temperature with high efficiency from triple State shines, that is, shows the compound of electroluminescent phosphorescence rather than electroluminescent fluorescent, typically results in energy efficiency increase.It is suitable for this Purpose be first containing atomic number greater than 36 heavy atom compound.Preferably containing the d or f for meeting above-mentioned condition The compound of transition metal.Herein particularly preferably containing correspondingization of the 8th to 10 race's element (Ru, Os, Rh, Ir, Pd, Pt) Close object.Suitable functional compounds are for example various complex compounds herein, such as example in 02/068435 A1, WO 02/ of WO 081488 A1, EP 1239526 is described in A2 and 2004/026886 A2 of WO.
The preferred compound that may be used as fluorescent illuminant is described by following instance.Preferred fluorescent illuminant is selected from such as Lower classification: single styryl amine, diphenylethyllene amine, triphenylethylene base amine, tetraphenyl ethylene base amine, styryl phosphine, styrene Base ether and arylamine.
Single styryl amine refers to containing a substituted or unsubstituted styryl group and at least one amine, preferably The compound of aromatic amine.Diphenylethyllene amine refers to containing there are two substituted or unsubstituted styryl groups and at least one The compound of amine, preferably aromatic amine.Triphenylethylene base amine refer to containing there are three substituted or unsubstituted styryl group and The compound of at least one amine, preferably aromatic amine.Tetraphenyl ethylene base amine refers to containing there are four substituted or unsubstituted styrene The compound of base group and at least one amine, preferably aromatic amine.The styryl group is particularly preferably Stilbene, can also be into One step is substituted.To define corresponding phosphine and ether in a manner of as amine.Arylamine or aromatic amine in the sense of the present invention be Refer to containing there are three be bound directly to the substituted or unsubstituted aromatics of nitrogen or the compound of heteroaromatic ring system.These aromatics or heteroaryl At least one of race's ring system is preferably condensed ring system preferably at least 14 aromatic ring atoms.Its preferred embodiment is aromatics Anthranylamine, aromatics anthradiamine, aromatics pyrene amine, aromatics pyrene diamines, aromatics lettuce amine or aromatics lettuce diamines.Aromatics anthranylamine refers to one of them The compound that diarylamino groups are directly preferably bonded at 9 with anthryl group.Aromatics anthradiamine refers to two of them diaryl Amino group is directly with anthryl group preferably in 2,6 or 9,10 compounds being bonded.Aromatics is defined in similar mode Pyrene amine, pyrene diamines, lettuce amine and lettuce diamines, wherein the diarylamino groups preferably with pyrene at 1 or 1,6 be bonded.
Other preferred fluorescent illuminants are selected from indeno fluorenamine or indeno fluorenediamine, are especially described in WO 2006/ In 122630；Benzo indeno fluorenamine or benzo indeno fluorenediamine, are especially described in WO 2008/006449；With dibenzo indenes And fluorenamine or dibenzo indeno fluorenediamine, it is especially described in WO 2007/140847.
May be used as fluorescent illuminant from the example of styryl aminated compounds be substituted or unsubstituted three Stilbene Amine is described in WO 2006/000388, WO 2006/058737, WO 2006/000389, WO 2007/065549 and WO Dopant in 2007/115610.Two (styryl) benzene and two (styrene) base biphenyl derivatives are described in US 5121029 In.Other styryl amine are found in 2007/0122656 A1 of US.
Particularly preferred styrylamine compounds are the compounds and DE of formula EM-1 described in 7250532 B2 of US The compound of formula EM-2 described in 10 2,005 058557 A1:
Particularly preferred triarylamine compound be 1,583,691 08/053397 A and 6251531 B1 of US of A, JP of CN, 1,957,606 200,8/0,113,101 2006/210830 A, WO 2008/006449 and DE of A1, US of A1, US of EP The compound and its derivative of formula EM-3 to EM-15 disclosed in 102008035413:
The other preferred compounds that may be used as fluorescent illuminant are selected from naphthalene, anthracene, aphthacene, benzanthracene, benzophenanthrene (DE 10 2,009 005746), fluorenes, fluoranthene, two indenos, indeno, phenanthrene, (2007/0252517 A1 of US), pyrene, lettuce, bull's eye Alkene, coronene, tetraphenyl cyclopentadiene, Pentaphenylcyclopentadiene, fluorenes, spiro fluorene, rubrene, cumarin (US 4769292, US 6020078,2007/0252517 A1 of US), pyrans,Azoles, benzoAzoles, benzothiazole, benzimidazole, pyrazine, cinnamic acid Ester, diketopyrrolo-pyrrole, acridone and quinacridone (2007/0252517 A1 of US) derivative.
In anthracene compound, the anthracene that particularly preferably 9,10- replaces, for example, 9,10- diphenylanthrancenes and 9, the bis- (benzene of 10- Ethyl-acetylene base) anthracene.Bis- (the 9'- acetenyl anthryl) benzene of 1,4- are also preferred dopant.
It is also preferred that rubrene, cumarin, rhodamine, quinacridone such as DMQA (=N, N'- dimethyl quinacridine Ketone), dicyano first subunit pyrans such as DCM (=4- (dicyano second subunit) -6- (4- dimethylaminostyryl -2- first Base) -4H- pyrans), thiapyran, polymethine, pyransAnd thiapyranThe derivative of salt, two indenos and indeno.
Blue luminescence body is preferably poly aromatic compound, for example, 9,10- bis- (2- naphthyl anthracenes) and other anthracenes are derivative Object, aphthacene, xanthene, such as 2, the bis- (9- ethyl -3- carbazole ethylene of 5,8,11- tetra-terts, benzene subunit such as 4,4'- Subunit) -1,1'- biphenyl, fluorenes, fluoranthene, aryl pyrene (2006/0222886 A1 of US), fragrant subunit ethylene subunit (US 5121029, US 5130603), bis- (azine) imines-boron compounds (2007/0092753 A1 of US), bis- (azine) first subunit chemical combination The derivative of object and quinoline-2-ketone compound.
Other preferred blue luminescence bodies are described in C.H.Chen etc.: " the latest developments of electroluminescent organic material (Recent developments in organic electroluminescent materials)”Macromol.Symp. (macromolecular seminar), 125, (1997) 1-48 and " latest developments (Recent of molecule organic electroluminescent material and device progress of molecular organic electroluminescent materials and devices)” Mat.Sci.and Eng.R (Materials Science and Engineering report), 39 (2002), in 143-222.
Other preferred blue luminescence bodies are hydrocarbon disclosed in DE 102008035413.
The preferred compound that may be used as phosphorescent emitter is illustrated description below.
WO 00/70655、WO 01/41512、WO 02/02714、WO 02/15645、EP 1191613、EP 1191612, EP 1191614 and WO 2005/033244 disclose the example of phosphorescent emitter.In general, according to existing skill Art for sum all phosphorescent complexes known to the technical staff of field of organic electroluminescence of phosphorescent OLED be all it is suitable, And those skilled in the art will use other phosphorescent complexes without creative efforts.
Phosphorescent metal complex preferably comprises Ir, Ru, Pd, Pt, Os or Re, more preferable Ir.
Preferred ligand is 2- phenylpyridine derivative, 7,8- benzoquinoline derivative, 2- (2- thienyl) pyridine derived Object, 2- (1- naphthalene) pyridine derivate, 1- octaverine, 3- octaverine or 2- phenylchinoline are derivative Object.All these compounds can be substituted, such as be replaced by fluorine, cyano and/or trifluoromethyl substituent for blue light.Auxiliary is matched Body is preferably acetylacetonate or pyridine carboxylic acid.
Particularly, the complex compound of Pt or Pd and the tetradentate ligands of formula EM-16 is suitable.
The compound of formula EM-16 is described in greater detail in 2007/0087219 A1 of US, wherein in order to explain in above formula Substituent group and label, for disclosure purposes refer to the specification.In addition, having the Pt- porphyrin complex (US for expanding ring system 2009/0061681 A1) and Ir complex compound, such as 2,3,7,8,12,13,17,18- octaethyl -21H, 23H- porphyrin-Pt (II), tetraphenyl-Pt (II) Tetrabenzoporphyrin (2009/0061681 A1 of US), cis--bis- (2- phenylpyridine root conjunction-N, C2') Pt (II), cis--bis- (2- (2'- thienyl) pyridine root conjunction-N, C3') Pt (II), cis--bis- (2- (2'- thienyl) quinoline root Conjunction-N, C5') Pt (II), (2- (4,6- difluorophenyl) pyridine root conjunction-N, C2') Pt (II) (acetylacetonate) or three (2- benzene Yl pyridines root conjunction-N, C2') Ir (III) (=Ir (ppy)3, green light), bis- (2- phenylpyridine root conjunction-N, C2) Ir (III) (acetyl Acetone solvate) (=Ir (ppy)2Acetylacetonate, green light, US 2001/0053462 A1, Baldo, Thompson etc., Nature (nature), 403, (2000), 750-753), bis- (1- phenyl isoquinolin quinoline root conjunction-N, C2') (2- phenylpyridine root conjunction-N, C2') iridium (III), bis- (2- phenylpyridine root conjunction-N, C2') (1- phenyl isoquinolin quinoline root conjunction-N, C2') iridium (III), bis- (2- (2'- benzene Bithiophene base) pyridine root conjunction-N, C3') iridium (III) (acetylacetonate), bis- (2- (4', 6'- difluorophenyl) pyridine root conjunctions- N,C2') iridium (III) (pyridine carboxylic acid salt) (FIrpic, blue light), bis- (2- (4', 6'- difluorophenyl) pyridine root conjunction-N, C2')Ir (III) (four (1- pyrazolyl) borates), three (2- (biphenyl -3- base) -4- tert .-butylpyridine) iridium (III), (ppz)2Ir (5phdpym)(US 2009/0061681 A1)、(45ooppz)2Ir (5phdpym) (2009/0061681 A1 of US), 2- benzene The derivative of yl pyridines-Ir complex compound, (=bis- (2- phenylchinoline base-N, C for example, PQIr2') acetylacetonate iridium (III)), three (2- phenyl isoquinolin quinoline root conjunction-N, C) Ir (III) (feux rouges), bis- (2- (2'- benzo [4,5-a] thienyl) pyridines Root conjunction-N, C3) Ir (acetylacetonate) ([Btp2Ir (acac)], feux rouges, Adachi etc., Appl.Phys.Lett. (apply object Flash report of science), 78 (2001), 1622-1624).
That equally suitable is trivalent lanthanide series such as Tb3+And Eu3+Complex compound (J.Kido etc., Appl.Phys.Lett. (applied physics flash report), 65 (1994), 2124；Kido etc., Chem.Lett. (Chemistry Letters), 657,1990；2007/0252517 A1 of US) or Pt (II), Ir (I), Rh (I) and two mercaptide of Maleic nitrile phosphorescence be complexed Object (Johnson etc., JACS 105,1983,1795), Re (I) three carbonyls-diimine complex compound (especially Wrighton, JACS 96,1974,998), complex compound (Ma etc., Synth.Metals of Os (II) and cyano ligand and bipyridyl or phenanthroline ligand (synthesis metal), 94,1998,245).
Other phosphorescent emitters with tridentate ligand are described in US 6824895 and US 10/729238.It glows Phosphorescent complexes are seen in US 6835469 and US 6830828.
Particularly preferred compound as the phosphorescent dopants especially compound of formula EM-17, is especially described in US 2001/0053462 A1 and Inorg.Chem. (inorganic chemistry), 2001,40 (7), 1704-1711；JACS 2001,123 (18), in 4304-4312 and its derivative.
Derivative is described in 7378162 B2, US 6835469 of US in B2 and 2003/253145 A of JP.
In addition, the 7238437 formula EM-18 to EM- described in A1 and EP 1348711 of B2, US 2009/008607 of US 21 compound and its derivative may be used as illuminator.
Quantum dot may also serve as illuminator, these materials are disclosed in detail in 2011/076314 A1 of WO.
The compound as material of main part especially together with luminophor includes the material from multiple material classifications Material.
Material of main part usually has the band gap between biggish HOMO and LUMO compared to luminiferous material used.This Outside, preferred material of main part shows the characteristic of hole transport or electron transport material.In addition, material of main part can have electronics Both transmission and hole transporting properties.
Material of main part is also referred to as host material in some cases, especially if material of main part and phosphorescent emitter exist When being applied in combination in OLED.
The preferred material of main part being especially used together with fluorescent dopants or total material of main part classification chosen from the followings: Oligomeric virtue subunit (such as 2,2', 7,7'- tetraphenyl spiral shell, two fluorenes or dinaphthyl anthracene according to EP 676461), especially containing thick Close the oligomeric fragrant subunit of aromatic group, such as anthracene, benzanthracene, benzophenanthrene (DE 10 2,009 005746, WO 2009/ 069566), phenanthrene, aphthacene, coronene, lettuce, fluorenes, spiro fluorene, phthalein simultaneously, naphtho-, decacyclene, rubrene, oligomeric virtue is sub- Base ethylene subunit (such as bis- (2,2- the diphenylacetylene) -1,1'- biphenyl of DPVBi=4,4'- or spiral shell-according to EP 676461 DPVBi), the metal complex of polypody metal complex (such as according to WO 04/081017), especially 8-hydroxyquinoline, such as AlQ3(=tri- (8-hydroxyquinoline) aluminium (III)) or bis- (conjunction of 2- methyl -8- quinoline root) -4- (conjunction of phenylphenol root) aluminium, and Imidazoles chelate (2007/0092753 A1 of US) and quinoline-metal complex, aminoquinoline-metal complex, benzoquinoline- Metal complex, hole-conductive compound (such as according to WO 2004/058911), electronics conducting compound, especially ketone, oxygen Change (such as according to WO 2005/084081 and WO 2005/084082) such as phosphine, sulfoxides, atropisomer (such as according to WO 2006/048268), boronic acid derivatives (such as according to WO 2006/117052) or benzanthracene are (such as according to WO 2008/ 145239)。
May be used as material of main part or altogether material of main part particularly preferred compound classification chosen from the followings: comprising anthracene, The atropisomer of the oligomeric fragrant subunit or these compounds of benzanthracene and/or pyrene.Oligomeric fragrant subunit in the sense of the present invention It is intended to refer to the compound that wherein at least three aryl or fragrant subunit group bond together.
Preferred material of main part in particular selected from formula (H-1) compound,
Ar4-(Ar5)p-Ar6 (H-1)
Wherein Ar4、Ar5、Ar6Be identical or differently at each occurrence aryl with 5 to 30 aromatic ring atoms or Heteroaryl groups, the group can be optionally substituted, and p indicates the integer in 1 to 5 range；If p=1, Ar4、Ar5With Ar6In pi-electron summation be at least 30, be at least 36 if p=2, and be at least 42 if p=3.
In the compound of formula (H-1), group Ar5Particularly preferably represent anthracene, and group Ar4And Ar6At 9 and 10 Position bonding, wherein these groups can be optionally substituted.Very particularly preferably, group Ar4And/or Ar6At least one of be thick Aryl group is closed, selected from 1- naphthalene or 2- naphthalene, 2- phenanthryl, 3- phenanthryl or 9- phenanthryl or 2- benzo anthryl, 3- benzanthracene Base, 4- benzo anthryl, 5- benzo anthryl, 6- benzo anthryl or 7- benzo anthryl.Compound based on anthracene is described in US 2007/ In 2007/0252517 A1 of 0092753 A1 and US, such as 2- (4- aminomethyl phenyl) -9,10- bis- (2- naphthalene) anthracene, 9- (2- naphthalene Base) -10- (1,1'- xenyl) anthracene and 9,10- bis- [4- (2,2- diphenylacetylene) phenyl] anthracenes, 9,10- diphenylanthrancene, 9, Bis- (phenylene-ethynylene) anthracenes of 10- and bis- (the 9'- acetenyl anthryl) benzene of 1,4-.It is also preferable that containing there are two the chemical combination of anthracene unit Object (2008/0193796 A1 of US), such as 10, bis- [1,1', 4', 1 "] terphenyl -2- base -9, the 9'- dianthracenes of 10'-.
Other preferred compounds are the derivatives of following substance: arylamine, styryl amine, fluorescein, diphenyl fourth Diene, tetraphenylbutadiene, cyclopentadiene, tetraphenyl cyclopentadiene, Pentaphenylcyclopentadiene, cumarin,Diazole, double benzosOxazoline,Azoles, pyridine, pyrazine, imines, benzothiazole, benzoAzoles, benzimidazole (2007/0092753 A1 of US) example Such as 2,2', 2 "-(1,3,5- benzene subunit) three [1- phenyl -1H- benzimidazole], aldazine, Stilbene, styryl virtue ylidene derivatives Such as 9, the fragrant ylidene derivatives (US of bis- [4- (2, the 2- diphenylacetylene) phenyl] anthracenes of 10- and two (styryls) 5121029), diphenylethlene, vinyl anthracene, diaminocarbazole, pyrans, thiapyran, diketopyrrolo-pyrrole, polymethine, cortex cinnamomi Acid esters and fluorescent dye.
The particularly preferably derivative of arylamine and styryl amine, such as the TNB (bis- [N- (1- naphthalene)-of=4,4'- N- (2- naphthalene) amino] biphenyl).Metal-class oxyquinoline complex compound, such as LiQ or AlQ3, may be used as total main body.
The compound preferably with oligomeric fragrant subunit as matrix is disclosed in US 2003/0027016 A1, US 7326371 B2、US 2006/043858 A、WO 2007/114358、WO 2008/145239、JP 3148176 B2、EP 1009044、US 2004/018383、WO 2005/061656 A1、EP 0681019B1、WO 2004/013073A1、US 5077142, in WO 2007/065678 and DE 102009005746, wherein particularly preferred formula H-2 to H-8 is retouched It states.
Furthermore, it is possible to which the compound for being used as main body or matrix includes the material being used together with phosphorescent emitter.
These compounds for the structural unit being also used as in polymer include CBP (the bis- carbazyl biphenyl of N, N-), click Zole derivatives (such as according to WO 2005/039246, US 2005/0069729, JP 2004/288381, EP 1205527 or WO 2008/086851), azepine carbazole is (such as according to EP 1617710, EP 1617711, EP 1731584 or JP 2005/ 347160), ketone (such as according to WO 2004/093207 or according to DE 102008033943), phosphine oxide, sulfoxide and sulfone (such as According to WO 2005/003253), oligocene subunit, aromatic amine (such as according to US 2005/0069729), bipolarity host material (such as according to WO 2007/137725), silane (such as according to WO 2005/111172), 9,9- diaryl fluorene derivatives (such as According to DE 102008017591), azepine boron heterocyclic pentylene or borate (such as according to WO 2006/117052), triazine is spread out Biological (such as according to DE 102008036982), indolocarbazole derivatives (such as according to WO 2007/063754 or WO 2008/056746), indenocarbazole derivatives (such as according to DE 102009023155 and DE 102009031021), diaza Phosphene derivative (such as according to DE 102009022858), triazole derivative,Azoles andZole derivatives, imidazoles Derivative, poly- aromatic yl paraffin derivative, pyrazoline derivative, pyrazolone derivative, two (styryl) pyrazines derivatives, thiophene It mutters dioxide derivative, phenylenediamine derivative, aromatic uncle amine, styryl amine, the chalcone derivative that amino replaces, Yin Diindyl, hydazone derivative, stilbene derivative, silazane derivatives, aromatics diformazan ylidene compounds, carbodiimide derivative, 8- hydroxyl quinoline The metal complex of quinoline derivant such as AlQ3, can also contain triaryl amino-phenol ligand (US 2007/0134514 A1), metal complex/polysilane compound and thiophene, benzothiophene and dibenzothiophene derivatives.
The example of preferred carbazole derivates is mCP (bis- carbazyl benzene of=1,3-N, N- (=9,9'- (1,3- benzene subunit) Double -9H- carbazoles)) (formula H-9), CDBP (=9,9'- (2,2'- dimethyl [1,1'- biphenyl] -4,4'- diyl) double -9H- clicks Azoles), bis- (bis- carbazyl of N, the N'-) benzene of 1,3- (bis- (carbazole -9- base) benzene of=1,3-), PVK (polyvinyl carbazole), 3,5- bis- (9H- carbazole -9- base) biphenyl and CMTTP (formula H-10).Particularly preferred compound be disclosed in 2007/0128467 A1 of US and In 2005/0249976 A1 of US (formula H-11 and H-13).
Preferred four aryl-Si compound is e.g., as disclosed in US 2004/0209115, US 2004/0209116, US 2007/0087219 A1 and H.Gilman, E.A.Zuech, Chemistry&Industry (chemistry and industry) (Britain's human relations Earnestly), in 1960,120.
Particularly preferred four aryl-Si formula H-14 to H-21 description.
The particularly preferred compound from the 4th group for being used to prepare the matrix of phosphorescent dopants is especially disclosed in DE 102009022858, in DE 102009023155, EP 652273 B1, WO 2007/063754 and WO 2008/056746, In particularly preferred formula H-22 to H-25 description.
About can functional compounds used according to the invention and may be used as material of main part, especially preferably contain There is the substance of at least one nitrogen-atoms.These preferably include aromatic amine, pyrrolotriazine derivatives and carbazole derivates.Therefore, carbazole spreads out Biology especially shows surprising high efficiency.Pyrrolotriazine derivatives lead to the unexpected long-life of electronic device.
It furthermore can it is preferable to use a variety of different host materials for being in form of mixtures, especially at least a kind of electronics to pass Lead host material and at least one hole-conductive host material.It is also preferred that transmitting host material and electrically inert using charge The mixture of host material, the electrically inert host material participate in charge not on significance degree participating in charge transmission and pass It is defeated, as example described in WO 2010/108579.
Furthermore the transition improved from singlet state to triplet can be used and have the function of illuminator characteristic for carrying Compound and improve these compounds phosphorescent characteristics compound.Particularly, be suitable for the purpose is carbazole and bridge joint Carbazole dimerization body unit, as example described in 2004/113468 A1 of WO 2004/070772 A2 and WO.It is also suitable for This purpose is ketone, phosphine oxide, sulfoxide, sulfone, silane derivative and similar compound, such as example in 2005/040302 A1 of WO Described in.
N-type dopant herein refers to reducing agent, i.e. electron donor.The preferred embodiment of n-type dopant is W (hpp)4And root According to other electron rich metal complexes of 2005/086251 A2 of WO, P=N compound (such as WO 2012/175535 A1, WO 2012/175219 A1), naphthylene carbodiimide (such as 2012/168358 A1 of WO), fluorenes (such as WO 2012/031735 A1), free radical and two free radicals (such as 1,837,926 2007/107306 A1 of A1, WO of EP), pyridine (such as EP 2452946 2463927 A1 of A1, EP), N- heterocyclic compound (such as 2009/000237 A1 of WO) and acridine and azophenlyene (such as US 2007/145355 A1)。
In addition, the preparation may include wide bandgap material as functional material.Wide bandgap material refers in US 7,294, Material in 849 disclosure meaning.These systems show particularly advantageous performance data in electroluminescent device.
Compound as wide bandgap material can preferably have 2.5eV or bigger, preferably 3.0eV or bigger, special Preferably 3.5eV or bigger band gap.Band gap especially minimum can not account for by highest occupied molecular orbital (HOMO) and molecule The energy level of track (LUMO) calculates.
In addition, the preparation may include hole barrier materials (HBM) as functional material.Hole barrier materials are indicated more The material of hole (positive charge) transmission is prevented or minimized in coating systems, especially if the material is with neighbouring luminescent layer or hole When the layer form arrangement of conducting shell.In general, hole barrier materials compared to the hole mobile material in adjacent layer have compared with Low HOMO energy level.Hole blocking layer is usually placed between the luminescent layer and electron transfer layer in OLED.
Any of hole barrier materials substantially can be used.In addition to other holes resistance of the other place descriptions of the application Except obstructing material, advantageous hole barrier materials are metal complex (US2003/0068528), for example, bis- (2- methyl -8- quinolines Quinoline root closes) (conjunction of 4- phenylphenol root) aluminium (III) (BAlQ).For this purpose, same-three (1- Phenylpyrazole root conjunction-of using face formula N, C2) iridium (III) (Ir (ppz)3)(US 2003/0175553 A1).It can also use phenanthroline derivative, such as BCP, Or phthalimide, such as TMPP.
In addition, advantageous hole barrier materials are described in WO 00/70655 A2, WO 01/41512 and WO 01/93642 In A1.
In addition, the preparation may include electron-blocking materials (EBM) as functional material.Electron-blocking materials are indicated more The material of electron-transport is prevented or minimized in coating systems, especially if the material is with neighbouring luminescent layer or electronic conductive layer When layer form arrangement.In general, electron-blocking materials have higher LUMO compared to the electron transport material in adjacent layer Energy level.
Any of electron-blocking materials substantially can be used.In addition to other electronics resistance of the other place descriptions of the application Except obstructing material, advantageous electron-blocking materials are transition metal complexes, for example, Ir (ppz)3(US 2003/0175553)。
The electron-blocking materials can be preferably selected from amine, triarylamine and its derivative.
In addition, if the functional compounds that may be used as the organic functional material in the preparation are low molecular weight chemical combination Object, then it preferably has≤3,000g/mol, more preferably≤2,000g/mol and most preferably≤1,000g/mol molecular weight.
In addition, being especially envisaged that the functional compounds characterized by high glass-transition temperature.In this respect, Ke Yiyong The particularly preferred functional compounds for making the organic functional material in the preparation are that have to be measured as >=70 according to DIN 51005 DEG C, preferably >=100 DEG C, more preferably >=those of 125 DEG C and glass transition temperature most preferably >=150 DEG C.
The preparation also may include polymer as organic functional material.It is described above as the chemical combination of organic functional material Object usually has relatively low molecular weight, can also be with mixed with polymers.Equally these compounds can be covalently incorporated to poly- It closes in object.Especially for by reactive leaving group such as bromine, iodine, chlorine, boric acid or borate or by reactive polymerizable group The compound that group such as alkene or oxetanes replace, this is feasible.These may be used as manufacture corresponding oligomer, The monomer of dendritic macromole or polymer.Oligomeric or polymerization herein is preferably via halogen functional group or boric acid functional group or warp It is carried out by polymerizable groups.In addition, crosslinked polymer can be made by such group.Compound according to the present invention and poly- Closing object may be used as crosslinking or uncrosslinked layer.
The polymer that may be used as organic functional material usually contains described in the context of above compound Unit or structural unit, especially if 02/077060 A1, WO 2005/014689 of WO is in A2 and 2011/076314 A1 of WO Those of disclose and list extensively.These are incorporated by reference into the application.Functional material can be originated from for example following classification:
1st group: the structural unit of hole injection and/or hole transporting properties can be generated；
2nd group: the structural unit of electron injection and/or electron transport property can be generated；
3rd group: by the structural unit of the property combination described in the 1st group and the 2nd group；
4th group: the structural unit with the characteristics of luminescence, particularly phosphorescence groups；
5th group: improving the structural unit of the transition from so-called singlet state to triplet；
6th group: influencing the form of resulting polymers or the structural unit of luminescent color；
7th group: being typically used as the structural unit of skeleton.
Structural unit herein can also have a various functions, thus clearly divide be not necessarily it is advantageous.For example, the 1st The structural unit of group also is used as skeleton.
There are hole transport or hole-injection characteristics as organic functional material containing the structural unit from the 1st group Polymer preferably contain the unit corresponding to above-mentioned hole transport or hole-injecting material.
Other preferred 1st group of structural units be for example triarylamine, benzidine, four aryl-p-phenylenediamine, carbazole, Azulene, thiophene, pyrroles and furan derivatives and the other heterocyclic compound containing O, S or N with high HOMO.These arylamines Preferably there is the HOMO higher than -5.8eV (relative to vacuum level), particular higher than -5.5eV with heterocyclic compound.
It is preferred that especially having the polymer of hole transport or hole-injection characteristics, contain at least one following formula HTP- 1 repetitive unit:
Wherein symbol has following meanings:
Ar1It is in each case singly-bound or monocycle or polycyclic virtue identical or differently for different repetitive units Base group can be optionally substituted；
Ar2It is in each case monocycle or polycyclic aryl group identical or differently for different repetitive units, It can optionally be substituted；
Ar3It is in each case monocycle or polycyclic aryl group identical or differently for different repetitive units, It can optionally be substituted；
M is 1,2 or 3.
The particularly preferably repetitive unit of formula HTP-1 is selected from the unit of formula HTP-1A to HTP-1C:
Wherein symbol has following meanings:
RaIt is H identical or differently at each occurrence, substituted or unsubstituted aromatics or heteroaromatic group, alkyl, ring Alkyl, alkoxy, aralkyl, aryloxy group, arylthio, alkoxy carbonyl, silicyl or carboxylic group, halogen atom, cyano Group, nitryl group or hydroxyl group；
R is 0,1,2,3 or 4, and
S is 0,1,2,3,4 or 5.
It is preferred that especially having the polymer of hole transport or hole-injection characteristics, contain at least one following formula HTP- 2 repetitive unit:
-(T1)c-(Ar7)d-(T2)e-(Ar8)f- HTP-2
Wherein symbol has following meanings:
T1And T2Independently selected from thiophene, selenophen, thieno [2,3-b] thiophene, thieno [3,2-b] thiophene, dithieno Thiophene, pyrroles and aniline, wherein these groups can be by one or more group RbReplace；
RbAt each occurrence independently selected from halogen ,-CN ,-NC ,-NCO ,-NCS ,-OCN ,-SCN ,-C (=O) NR0R00,-C (=O) X ,-C (=O) R0,-NH2,-NR0R00,-SH ,-SR0,-SO3H ,-SO2R0,-OH ,-NO2,-CF3,-SF5, appoint Substituted silicyl is selected, carbyl or hydrocarbyl group with 1 to 40 carbon atom, the group can be optionally substituted And it can be optionally containing one or more hetero atoms；
R0And R00It is H or optionally substituted carbyl or the alkyl base with 1 to 40 carbon atom each independently Group, the group can optionally be substituted and can be optionally containing one or more hetero atoms；
Ar7And Ar8Indicate that monocycle or polycyclic aryl or heteroaryl group, the group can optionally be taken independently of one another Generation and it can optionally be bonded to 2,3 of one or two adjacent thiophene or selenophen group；
C and e is 0,1,2,3 or 4 independently of one another, wherein 1 < c+e≤6；
D and f is 0,1,2,3 or 4 independently of one another.
The preferred embodiment of polymer with hole transport or hole-injection characteristics is especially described in WO 2007/131582 In 2008/009343 A1 of A1 and WO.
There is electron injection and/or electron-transport as organic functional material containing the structural unit from the 2nd group The polymer of characteristic preferably contains the unit corresponding to above-mentioned electron injection and/or electron transport material.
The 2nd group of other preferred structure units with electron injection and/or electron transport property derived from such as pyridine, Pyrimidine, pyridazine, pyrazine,Diazole, quinoline, quinoxaline and azophenlyene group and triarylborane group or it is other have it is low The heterocyclic compound containing O, S or N of lumo energy.2nd group these structural units preferably have less than -2.7eV (relative to true Unoccupied level), especially preferably less than -2.8eV LUMO.
The organic functional material may be preferred that the polymer containing the structural unit from the 3rd group, wherein improving empty The structural unit (i.e. the structural unit from the 1st group and the 2nd group) of cave and electron mobility is connected to each other directly.These are tied herein Some in structure unit may be used as illuminator, and wherein luminescent color is changeable, such as become green, red or yellow.Therefore, Their use for example generates other luminescent colors for the polymer by script blue light-emitting or broad-band illumination is advantageous.
The polymer with the characteristics of luminescence as organic functional material containing the structural unit from the 4th group is preferable Contain the unit for corresponding to above-mentioned luminiferous material.It is preferably the polymer containing phosphorescence groups, especially above-mentioned hair herein Light metal complex contains the corresponding unit for containing the 8th to 10 race's element (Ru, Os, Rh, Ir, Pd, Pt).
It is used as the poly- of organic functional material containing the 5th group of unit for improving the transition from so-called singlet state to triplet Closing object can be preferred for carrying phosphorescent compound, preferably contain the polymer of above-mentioned 4th group of structural unit.It herein can be with Use polymer triplet matrix.
It is suitable for the carbazole dimerization body unit of the especially carbazole and connection of the purpose, such as example in 10304819 A1 of DE With described in 10328627 A1 of DE.Be also suitable for this purpose be ketone, phosphine oxide, sulfoxide, sulfone and silane derivative and Similar compound, as described in such as 10349033 A1 of DE.Furthermore it is preferred that structural unit can derived from above in association with Compound described in the host material that phosphorescent compound is used together.
Other organic functional materials are preferably to contain the form for the polymer that has an impact and/or the 6th group of list of luminescent color The polymer of member.Other than above-mentioned polymer, these are that have at least one do not include the other aromatics in above-mentioned group Or those of other conjugated structures.Therefore, these groups are to charge carrier mobility, non-organic metal complex or substance State-triplet transition has little effect or does not influence.
Such structural unit can influence the form and/or luminescent color of resulting polymers.Depending on structure list Therefore member, these polymer are also used as illuminator.
In the case where fluorescence OLED, it is therefore preferred to the aromatic structure unit or two with 6 to 40 C atoms Phenylacetylene, Stilbene or bis- (styryls) fragrant ylidene derivatives unit, it is therein each to be replaced by one or more groups.Herein Particularly preferably using sub- derived from 1,4- benzene subunit, 1,4- naphthylene, 1,4- anthracene subunit or 9,10- anthracene subunit, 1,6- pyrene Base, 2,7- pyrene subunit or 4,9- pyrene subunit, 3,9- subunit or 3,10- subunit, 4,4'- biphenyl subunit, 4,4 "-terphenyls are sub- The fragrant subunit of base, 4,4'- connection -1,1'- naphthylene, 4,4'- tolans subunit, 4,4'- Stilbene subunit or 4,4 "-bis- (styryls) The group of derivative.
Polymer as organic functional material preferably comprises the 7th group of unit, preferably comprises and is typically used as skeleton Aromatic structure with 6 to 40 C atoms.
These especially include 4,5- dihydro pyrene derivatives, 4,5,9,10- tetrahydro pyrene derivatives, fluorene derivative, such as public It opens in US 5962631,2006/118345 A1 of WO 2006/052457 A2 and WO, 9,9- spirobifluorene derivatives, such as It is disclosed in 2003/020790 A1 of WO, 9,10- phenanthrene derivatives, e.g., as disclosed in 2005/104264 A1 of WO, 9,10- Dihydro phenanthrene derivative, e.g., as disclosed in 2005/014689 A2 of WO, 5, the 7- bright-coloured derivatives of dihydro-dibenzo oxepane with And cis and trans indeno fluorene derivative, e.g., as disclosed in 2004/113412 A2 of WO 2004/041901 A1 and WO, With dinaphthalene ylidene derivatives, e.g., as disclosed in 2006/063852 A1 of WO, and, for example, it is disclosed in WO 2005/056633 1,344,788 20,07/,043,495 20,05/,033,174 2003/099901 A1 and DE of A1, WO of A1, WO of A1, WO of A1, EP Other units in 102006003710.
Particularly preferably the 7th group of structural unit, be selected from fluorene derivative, e.g., as disclosed in US 5,962,631, In 2006/118345 A1 of WO 2006/052457 A2 and WO, spirobifluorene derivative, e.g., as disclosed in WO 2003/ In 020790 A1, benzfluorene, dibenzo fluorenes, benzothiophene and dibenzo fluorene group and its derivative, e.g., as disclosed in WO 2005/056633 A1, EP 1344788 is in A1 and 2007/043495 A1 of WO.
Particularly preferred 7th group of structural unit is indicated by general formula PB-1:
Wherein symbol and label have following meanings:
A, B and B' is also identical or differently respectively bivalent group for different repeat units, the group is preferably selected from- CRcRd-、-NRc-、-PRc-、-O-、-S-、-SO-、-SO2,-CO- ,-CS- ,-CSe- ,-P (=O) Rc,-P (=S) RcAnd- SiRcRd-；
RcAnd RdAt each occurrence independently selected from H, halogen ,-CN ,-NC ,-NCO ,-NCS ,-OCN ,-SCN ,-C (=O) NR0R00,-C (=O) X ,-C (=O) R0,-NH2,-NR0R00,-SH ,-SR0,-SO3H ,-SO2R0,-OH ,-NO2,-CF3,-SF5, appoint Substituted silicyl is selected, carbyl or hydrocarbyl group with 1 to 40 carbon atom, the group can be optionally substituted And it can be optionally containing one or more hetero atoms, wherein the group RcAnd RdThe fluorene group that can be optionally bonded with it is formed Tap bolt group；
X is halogen；
R0And R00It is H or optionally substituted carbyl or the alkyl base with 1 to 40 carbon atom each independently Group, the group are optionally substituted and can be optionally containing one or more hetero atoms；
G is independently 0 or 1 in each case, and h is independently 0 or 1 in each case, wherein in subunit G and the summation of h be preferably 1；
M is >=1 integer；
Ar1And Ar2Indicate that monocycle or polycyclic aryl or heteroaryl group, the group can optionally be taken independently of one another Generation and it can optionally be bonded to 7,8 or 8,9 of indeno fluorene group；And
A and b is 0 or 1 independently of one another.
If the group RcAnd RdThe fluorene group being bonded with these groups forms tap bolt group, then the group preferably indicates Two fluorenes of spiral shell.
The particularly preferably repetitive unit of formula PB-1 is selected from the unit of formula PB-1A to PB-1E:
Wherein RcWith above for meaning described in formula PB-1, r is 0,1,2,3 or 4, and ReWith with group RcPhase Same meaning.
RePreferably-F ,-Cl ,-Br ,-I ,-CN ,-NO2,-NCO ,-NCS ,-OCN ,-SCN ,-C (=O) NR0R00,-C (= O) X ,-C (=O) R0,-NR0R00, optionally substituted silicyl, the virtue with 4 to 40, preferably 6 to 20 C atoms Base or heteroaryl groups, or the straight chain with 1 to 20, preferably 1 to 12 C atom, branch or cricoid alkyl, alcoxyl Base, alkyl-carbonyl, alkoxy carbonyl, alkyl carbonyl oxy or alkoxy carbonyloxy group group, wherein one or more hydrogen atoms can appoint Choosing is replaced by F or Cl, and group R0、R00Have with X above for meaning described in formula PB-1.
The particularly preferably repetitive unit of formula PB-1 is selected from the unit of formula PB-1F to PB-1I:
Wherein symbol has following meanings:
L is H, the alkyl or alkoxy base of halogen or the optionally fluorinated linear chain or branched chain with 1 to 12 C atom, And it is preferred that representing H, F, methyl, isopropyl, tert-butyl, n-pentyloxy or trifluoromethyl；And
L' is the alkyl or alkoxy base of the optional fluorinated linear chain or branched chain with 1 to 12 C atom, and preferably Represent n-octyl or n-octyloxy.
In order to implement the present invention, the preferably polymer of the structural unit containing more than one above-mentioned 1st to 7 group. Furthermore it may be provided that, the polymer preferably comprises the more than one structural unit from said one group, that is, includes The mixture of structural unit selected from a group.
It is particularly preferred in particular, in addition to it is at least one have the characteristics of luminescence, preferably at least a kind of knot of phosphorescence groups Except structure unit (the 4th group), also contain the polymer of at least one the above-mentioned 1st to 3,5 or 6 group other of structural unit, In these structural units be preferably selected from the 1st to 3 group.
The ratio of various types of other group (if there is in polymer) can be in wide in range range, and wherein these are It is well known by persons skilled in the art.If (it is selected from the above-mentioned 1st to 7 to a kind of classification present in polymer in each case The structural unit of group) ratio mole % preferably in each case >=5, particularly preferably in each case >=10 mole %, It then can achieve astonishing advantage.
The preparation of the copolymer to emit white light is especially described in detail in 10343606 A1 of DE.
In order to improve dissolubility, the polymer can contain corresponding group.It is preferred that may be provided that, the polymer Containing substituent group, so that there are an average of at least 2 non-aromatic carbon atoms for each repetitive unit, particularly preferably at least four is simultaneously And especially preferably at least eight non-aromatic carbon atom, wherein average value is related to number average.Single carbon atom can be by example herein As O or S is replaced.However, special ratios, optionally all repetitive units can not include the substitution containing non-aromatic carbon atom Base.It is preferably short chain substituent herein, because the layer that long chain substituents can obtain usable organic functional material has Adverse effect.The substituent group contains at most 12 carbon atoms, preferably up to 8 carbon atoms and especially excellent preferably in straight chain Select at most 6 carbon atoms.
The polymer as organic functional material can be random, alternately or regional rule copolymer, embedding according to the present invention The combination of section copolymer or these copolymer forms.
In another embodiment, the polymer as organic functional material can be the non-conjugated polymeric with side chain Object, wherein the embodiment is especially important for the phosphorescent OLED based on polymer.In general, phosphorescent polymer can be with By the free-radical polymerized acquisition of vinyl compound, wherein these vinyl compounds contain at least one and shine with phosphorescence The unit of body and/or at least one charge passing unit are such as especially disclosed in 7250226 B2 of US.Other phosphorescence polymerizations Object is especially described in 20,07/,211,243 20,07/,197,574 7250226 B2 and JP 2007/059939 of A2, US of A2, JP of JP In A.
In another preferred embodiment, non-conjugated polymeric object contains skeleton unit, by spacer unit that This connection.The example of this triplet emitters of non-conjugated polymeric object based on skeleton unit is e.g., as disclosed in DE In 102009023154.
In another preferred embodiment, non-conjugated polymeric object is properly termed as fluorescent illuminant.Based on side chain Non-conjugated polymeric object the preferred fluorescent illuminant derivative containing anthracene or benzo anthryl group or these groups in the side chain, Wherein these polymer are disclosed in such as JP 2005/108556, JP 2005/285661 and JP 2003/338375.
These polymer usually may be used as electron-transport or hole mobile material, and wherein these polymer are preferably designed for Non-conjugated polymeric object.
In addition, it is used as the functional compounds of organic functional material in the preparation, it is excellent in the case where polymer compound Selecting has >=10,000g/mol, particularly preferably >=20,000g/mol and particularly preferably >=molecular weight M of 50,000g/molw。
The molecular weight M of polymer hereinwIt is preferred that in the range of 000 to 2,000,000g/mol, particularly preferably existing 10 In the range of 20,000 to 1,000,000g/mol and very particularly preferably in the range of 50,000 to 300,000g/mol. Molecular weight M is measured by the GPC (=gel permeation chromatography) relative to inner polystyrene standardw。
The publication quoted above for representation function compound is herein incorporated by reference this Shen for disclosure purposes Please in.
Preparation according to the present invention may include all organic functions necessary to manufacture the corresponding function layer of electronic device Material.If such as hole transport, hole injection, electron-transport or electron injecting layer are definitely to construct from a kind of functional compounds , then the preparation definitely includes this compound as organic functional material.If luminescent layer is including, for example, illuminator and base The combination of matter or material of main part, then the preparation definitely includes the mixture of illuminator and matrix or material of main part as organic function Energy material, such as the other place more detailed descriptions of the application.
Other than the component, preparation according to the present invention may include other additives and processing aid.These are especially Including surface reactive material (surfactant), lubricant and grease adjust the additive of viscosity, increase the addition of conductivity Agent, dispersing agent, hydrophobing agent, adhesion promotor, flow improving agent, defoaming agent, degasser can be reactivity or non-reacted Diluent, filler, auxiliary agent, processing aid, dyestuff, pigment, stabilizer, sensitizer, nano particle and inhibitor.
The invention further relates to a kind of methods for being used to prepare preparation according to the present invention, wherein will contain at least one carbonic acid At least the first organic solvent of ester group and at least one organic functional material for the functional layer that can be used for manufacturing electronic device are mixed It closes.
Preparation according to the present invention can be used for manufacturing wherein organic functional material and be present in the single or multi-layer structure in layer, As manufactured preferred electronics or photoelectron subassembly as needed for OLED.
Preparation of the invention is preferably used to form functional layer in substrate or a layer for being applied to substrate.The substrate There can be bank structure or not have bank structure.
Present invention is equally related to a kind of methods for manufacturing electronic device, wherein preparation according to the present invention is applied to substrate And it is dry.
The functional layer can be for example by substrate or being applied to the painting of layer overflow, a dip-coating, spraying, rotation of substrate Painting, silk-screen printing, letterpress, intaglio printing, rotary printing, roller coating, flexible version printing, hectographic printing or nozzle print, it is excellent Selection of land ink jet printing manufactures.
After the functional layer that preparation according to the present invention is applied to substrate or has been applied, can be dried step with Solvent is removed from above-mentioned continuous phase.In the period of drying preferably can carry out relatively long under relatively low temperature, to avoid bubble shape At and obtain uniform coating.Drying can preferably 80 to 300 DEG C, it is 150 to 250 DEG C and most preferably 160 to 200 DEG C more preferable At a temperature in the range of carry out.Here drying can be preferably 10-6Millibar within the scope of 2 bars, more preferable 10-2Millibar is to 1 Ba Fan In enclosing and most preferably 10-1It is carried out under millibar to the pressure within the scope of 100 millibars.During drying process, the temperature of substrate can To change between -15 DEG C to 250 DEG C.The dry duration depends on degree of drying to be achieved, wherein can be optionally A small amount of water is removed in the case where relatively high temperature is combined with the sintering preferably carried out.
Furthermore it may be provided that, which be repeated as many times, wherein forming similar and different functional layer.It herein can be with The crosslinking of functional layer is formed by prevent its dissolution, as disclosed in such as 0 637 899 A1 of EP.
The invention further relates to a kind of electronic devices, can be obtained by the method for manufacturing electronic device.
The invention further relates to a kind of electronic device, have the function of that at least one includes at least one organic functional material Layer can be obtained by the above-mentioned method for manufacturing electronic device.
Electronic device refers to the device including anode, cathode and at least one functional layer therebetween, wherein the functional layer packet Containing at least one organic or organo-metallic compound.
The organic electronic device is preferably organic electroluminescence device (OLED), polymer electroluminescent device (PLED), organic integrated circuits (O-IC), organic field effect tube (O-FET), Organic Thin Film Transistors (O-TFT), organic It is lighting transistor (O-LET), organic solar batteries (O-SC), organic photovoltaic (OPV) battery, organic optical detector, organic Photoreceptor, organic field quenching device (O-FQD), two pole of organic electric transducer, light-emitting electrochemical cell (LEC) or organic laser It manages (O- laser), more preferable organic electroluminescence device (OLED) or polymer electroluminescent device (PLED).
Active component is usually the organic or inorganic material introduced between the anode and the cathode, and wherein these active components are real Characteristic that is existing, maintaining and/or improve electronic device, such as its performance and/or its service life, for example, charge injection, charge transmission or Charge blocking material, but especially luminescent material and host material.Therefore it can be used for manufacturing having for the functional layer of electronic device Machine functional material preferably comprises the active component of electronic device.
Organic electroluminescence device is a preferred embodiment of the present invention.The organic electroluminescence device includes yin Pole, anode and at least one luminescent layer.
It is also preferable that using the mixture of two or more triplet emitters and matrix.With luminous compared with shortwave The triplet emitters of spectrum are used as the co-substrate with the triplet emitters compared with long wave luminescent spectrum herein.
The ratio of host material in luminescent layer in the case is preferably 50-99.9 volume % for fluorescent light-emitting layer, More preferably 80-99.5 volume % and most preferably 92-99.5 volume %, and be 85-97 body for phosphorescence luminescent layer Product %.
Correspondingly, the ratio of dopant is preferably 0.1-50 volume %, more preferably 0.5-20 body for fluorescent light-emitting layer Product % and most preferably 0.5-8 volume %, and be 3-15 volume % for phosphorescence luminescent layer.
The luminescent layer of organic electroluminescence device can also be covered comprising a variety of host materials (mixed-matrix system) and/or more The system of kind dopant.Also in this case, the dopant is usually the lesser material of ratio and the base in system Material is the material of large percentage in system.However, on rare occasion, the ratio of individual matrix material is smaller than in system The ratio of respective dopant agent.
Mixed-matrix system preferably comprises two or three of different host material, more preferable two different matrix materials Material.One of two kinds of materials are preferably the material with hole transporting properties herein and another material is with electron-transport spy The material of property.However, the required electron-transport and hole transporting properties of mixed-matrix component can also be combined mainly or entirely In single mixed-matrix component, wherein other mixed-matrix component meets other functions.Two different host materials are herein Can exist with the ratio of 1:50 to 1:1, preferably 1:20 to 1:1, more preferable 1:10 to 1:1 and most preferably 1:4 to 1:1.It is mixed Matrix system is closed to be preferred in phosphorescent organic electroluminescent device.Other details about mixed-matrix system are found in for example In WO 2010/108579.
In addition to these layers, organic electroluminescence device may also include other layer, such as one in each case Or multiple hole injection layers, hole transmission layer, hole blocking layer, electron transfer layer, electron injecting layer, exciton barrier-layer, electronics Barrier layer, charge generation layer (IDMC 2003, Taiwan；Session 21OLED(5),T.Matsumoto,T.Nakada, J.Endo,K.Mori,N.Kawamura,A.Yokoi,J.Kido,Multiphoton Organic EL Device Having Charge Generation Layer (the multi-photon OLED device with charge generation layer)) and/or organic or inorganic p/n Knot.One or more hole transmission layers can be for example with metal oxide such as MoO herein3Or WO3Or with (complete) fluorination electron deficient aromatics Compound carries out p-type doping, and/or one or more electron transfer layers can be by n-type doping.For having in electroluminescent device There is such as exciton blocking function and/or control the middle layer of charge balance, can equally be introduced between two luminescent layers.So And, it should be noted that each of these layers need not exist.When using preparation according to the present invention as defined above, These layers equally may be present.
In yet another embodiment of the present invention, the device includes multiple layers.Preparation according to the present invention herein may be used It is preferred for manufacturing hole transport, hole injection, electron-transport, electron injection and/or luminescent layer.
Therefore, the invention further relates to a kind of electronic devices comprising and at least three layers, but in a preferred embodiment In, all layers are produced from hole injection, hole transport, luminous, electron-transport, electron injection, charge barrier and/or charge Generating layer, and wherein at least one layer has passed through preparation used according to the invention and has obtained.The layer such as hole transport and/ Or the thickness of hole injection layer can be preferably in the range of 1 to 500nm, more preferably in the range of 2 to 200nm.
In addition, the device may include the layer being made of other low molecular weight compounds or polymer, not yet passing makes Applied with preparation according to the present invention.These can also be manufactured by evaporating low molecular weight compound in high vacuum.
In addition, such compound is preferably used, not instead of with pure material, with other with any required type Mixture (blend) the form use of polymer, oligomer, dendritic macromole or low molecular weight substance.These can for example change Kind characteristic electron itself shines.
In a preferred embodiment of the invention, preparation according to the present invention includes organic functional material, is used Make the material of main part or host material in luminescent layer.Other than material of main part or host material, on preparation here may include State illuminator.Here organic electroluminescence device may include one or more luminescent layers.If there is multiple luminescent layers, then this A bit preferably have multiple luminescence peaks between 380nm and 750nm, generally cause it is white luminous, can fluoresce or Phosphorescent a variety of luminophors are in the luminescent layer.Very particularly preferably be Three-tider architecture, wherein described three Layer is displayed in blue, green and orange or red shine (for basic structure, see, for example, WO 2005/011013).It emits white light Device is suitable as the backlight of such as LCD display or for general illumination application.
The arrangement in addition, multiple OLED can overlap each other, so that the efficiency about light output to be achieved further increases.
In order to improve the coupling output of light, the final organic layer on light exit side in OLED is for example also possible to nanometer bubble The form of foam reduces so as to cause total reflection ratio.
It is also preferable that following organic electroluminescence device, wherein one or more layers are applied by sublimation method, Wherein by being lower than 10 in vacuum sublimation unit-5Millibar, preferably shorter than 10-6Millibar, more preferably less than 10-7The pressure of millibar Vapor deposition is under power to apply the material.
Furthermore it may be provided that, one or more layers of electronic device according to the present invention pass through OVPD (organic vapors Deposition) technique or applied by means of carrier gas distillation, wherein 10-5Apply the material under millibar to 1 bar of pressure.
Furthermore it may be provided that, for example by spin coating from solution, or for example by means of any desired printing technology Silk-screen printing, flexible version printing, intaglio printing or hectographic printing, but particularly preferably LITI (light-initiated thermal imaging, thermal transfer) Or ink jet printing, to generate one or more layers of electronic device according to the present invention.
These layers can also by wherein do not use formula (I), (II), (IIa), (III) or (IIIa) compound work Skill applies.Here, although dissolving the functional material of layer to be applied, the function can not dissolved it is preferable to use orthogonal solvents It can the material layer to be applied to.
The device generally includes cathode and anode (electrode).Electrode (cathode, anode) is selected for purposes of the present invention, Enable their band as closely as possible can be corresponding with the band of adjacent organic layer, to ensure efficient electronics or hole note Enter.
The cathode preferably comprises metal complex, the metal with low work function, metal alloy or multilayered structure, described Metal alloy or multilayered structure include different metal for example alkaline-earth metal, alkali metal, main group metal or lanthanide series (such as Ca, Ba, Mg, Al, In, Mg, Yb, Sm etc.).In the case of the multi-layer structure, in addition to the metal, it is possible to use have relatively high Other metals of work function such as Ag and Ag nano wire (Ag NW), in this case, usually using the combination of metal, such as Ca/Ag or Ba/Ag.The thin of the material with high dielectric constant can also be introduced preferably between metallic cathode and organic semiconductor Middle layer.Be suitable for this purpose is, for example, alkali metal fluoride or alkali earth metal fluoride but it is also possible to be corresponding oxygen Compound (such as LiF, Li2O、BaF2, MgO, NaF etc.).The thickness degree of this layer be preferably 0.1 to 10nm, more preferable 0.2 to 8nm, and most preferably 0.5 to 5nm.
The anode preferably comprises the material with high work function.The anode preferably has to be greater than relative to vacuum The current potential of 4.5eV.It on the one hand, suitable for this purpose is that there is the metal of high redox potential, such as Ag, Pt or Au.Separately It on the one hand, can also preferably metal/metal oxide electrode (such as Al/Ni/NiOx、Al/PtOx).For some applications, electrode At least one of must be it is transparent, in favor of organic material irradiation (O-SC) or light coupling output (OLED/PLED, O- laser).Preferred structure uses transparent anode.Preferred anode material is electric conductivity mixed-metal oxides herein.It is special It You Xuanshi not indium tin oxide target (ITO) or indium zinc oxide (IZO).It is also preferable that electric conductivity adulterates organic material, especially Electric conductivity doped polymer, such as poly- (ethylidene propylenedioxythiophene) (PEDOT) and polyaniline (PANI) or these polymer spread out Biology.It is also preferable that the hole mobile material of p-type doping is applied to anode as hole injection layer, wherein suitable p-type Dopant is metal oxide, such as MoO3Or WO3, or (complete) fluorination electron deficient aromatic compounds.Other suitable p-type dopings Agent is HAT-CN (six cyano, six azepine benzophenanthrene) or the compound N PD9 from Novaled.Such layer simplifies Hole injection in material with low HOMO (i.e. with the HOMO of the larger value).
In general, all material such as according to the prior art for the layer can be used for other layers, and ability Field technique personnel will without creative efforts by these materials each with it is according to the present invention Combination of materials is in electronic device.
Depending on application, contact and finally quilt is arranged by correspondingly structuring in a way known in the device It is gas-tight seal, because the service life of the device sharply shortens in the presence of water and/or air.
Preparation according to the present invention and can thus obtained electronic device, particularly organic electroluminescence device, compared to The prior art is distinguished by following astonishing one or more of advantage:
1. the electronic device that preparation according to the present invention can be used to obtain is compared to the electronics device for using conventional method to obtain Part shows very high stability and very long service life.
2. conventional method processing can be used in preparation according to the present invention, so that cost advantage also may be implemented.
3. the organic functional material used in preparation according to the present invention is not by any specific limitation, so that of the invention Method can be used comprehensively.
4. the coating that preparation of the invention can be used to obtain shows excellent quality, especially in the uniformity side of coating Face.
These above-mentioned advantages are not accompanied by the damage of other Electronic Performances.
It should be pointed out that the modification of embodiment described in the present invention is fallen within the scope of the present invention.Unless expressly excluded, Otherwise each feature disclosed in the present invention can be provided identical, equivalent or similar purpose alternative features and replace.Therefore, it removes Non- to be otherwise noted, otherwise each feature disclosed in the present invention is considered as that the example of general series is either equivalent or similar Feature.
All features of the invention can be combined with each other in any way, unless certain features and/or step are mutually to arrange Reprimand.This is particularly suitable for preferred feature of the invention.Equally, the feature of optional combination can be used alone (rather than group It closes and uses).
The feature that should also be noted that many features, especially the preferred embodiment of the present invention, be in itself it is creative, A part without being regarded as merely embodiments of the present invention.For these features, can be required additionally or as current The substitution of each invention of protection seeks independent protection.
Introduction about technical movements disclosed by the invention can be extracted and combine with other embodiments.
The present invention is explained in greater detail below with reference to work example, but does not limit the invention.
Those skilled in the art will manufacture basis using this specification without creative efforts Other electronic devices of the invention, therefore the present invention can be implemented in entire scope claimed.
Work example
Work example presented below is carried out using device architecture shown in Fig. 1.The hole injection layer of all embodiments (HIL) it is prepared by ink-jet printing process with hole transmission layer (HTL) to realize required thickness.For luminescent layer, embodiment 1 With 2 used in respective solvent be listed in the table below in 2.
Table 2: solvent list used in Examples 1 and 2.
Using TA instrument ARG2 rheometer 10 to 1000s-1Range of shear rate in use 40mm parallel plate geometry knot The viscosity of structure measurement preparation and solvent.Measurement result is taken as 200 to 800s-1Average value, wherein precise control of temperature and shearing Rate.The viscosity provided in table 3 is the at a temperature of viscosity of every kind of preparation that measures at 25 DEG C.Every kind of solvent measurement is three times.Institute Stating viscosity number is the average value taken to the measurement result.
Preferably, the surface tension of organic solvent blend can in the range of 15 to 80mN/m, more preferably 20 to In the range of 60mN/m and most preferably in the range of 25 to 40mN/m.FTA (First Ten Angstrom) can be used 1000 contact angle angular instruments surface tension at 20 DEG C.The details of the method can be from Roger P.Woodward, Ph.D. " use stalagmometry (the Surface Tension Measurements Using the Drop of droplet profile method Shape Method) " announce First Ten Angstrom obtain.Preferably, sessile drop method can be used to determine surface tension. At room temperature progress of all measurements within the scope of 20 DEG C to 22 DEG C.For every kind of preparation, three drops are measured.End value is pair The measurement result is averaged.Periodically the tool is handed over for the various liquid with well-known surface tension Fork checks.
Examples 1 and 2 are manufactured by using identical structure, and wherein it is identical to realize to be injected printing by HIL and HTL Thickness.Solvent used in EML is different and details is listed in Table 3 below.
Table 3: the details of preparation used in Examples 1 and 2
The description of manufacturing process
The substrate of glass of the ITO and bank material that will be covered with pre- structuring in isopropanol, are then existed using ultrasonic wave It is cleaned in deionized water, it is then dry using air gun, then anneal 2 hours in 230 DEG C of heating plate.
Hole injection layer (HIL) ink jet printing of PEDOT-PSS (Clevios Al4083, Heraeus) will be used to base On bottom and it is dried in a vacuum.Then HIL is annealed 30 minutes in air at 185 DEG C.
At the top of HIL, ink jet printing hole transmission layer (HTL) is dried in a vacuum and at 210 DEG C in nitrogen atmosphere Middle annealing 30 minutes.As the material of hole transmission layer, polymer HTM-1 is used.The structure of polymer HTM-1 is as follows:
Green light emitting layer (G-EML) is dried in vacuo and anneals 10 points in nitrogen atmosphere at 160 DEG C also through ink jet printing Clock.Ink for green light emitting layer includes two kinds of material of main parts (i.e. HM-1 and HM-2) and one in all working embodiment Kind triplet emitters (EM-1).The material is used with following ratio: HM-1:HM-2:EM-1=2:2:1.These materials Structure is as follows:
All ink-jet printing process carry out under yellow light and environmental condition.
Then device is transferred in vacuum deposition chamber, uses thermal evaporation deposition hole blocking layer (HBL), electron transfer layer (ETL) and cathode (Al).Then the device is characterized in glove box.
As the hole barrier materials of hole blocking layer, ETM-1 is used.The material has a structure that
In electron transfer layer (ETL), the 50:50 mixture of ETM-1 and LiQ is used.LiQ is 8-hydroxyquinoline lithium.
In order to measure the OLED performance in terms of current density-luminous density-voltage performance, by by Keithley 2400 The scanning voltage for-the 5V to 25V that source measuring unit provides drives the device.OLED device is recorded by Keithley 2400SMU Voltage on part and the electric current by OLED device.Use the brightness of the photodiode detector part of calibration.With Keithley 6485/E picoammeter measures photoelectric current.For spectrum, luminance sensor is by being connected to Ocean Optics The glass fibre of USB2000+ spectrometer replaces.
Results and discussion
Embodiment 1
Use tert-butyl-phenyl carbonic ester as the solvent of luminescent layer, prepare have the layer through printing through ink jet printing OLED device.The structure of pixelation OLED device is glass/ITO/HIL (40nm)/HTM (20nm)/EML (60nm)/HBL (10nm)/ETL (40nm)/Al, thus in substrate prefabricated embankment to form pixelation device.In this case, green hair Luminescent material is dissolved in tert-butyl-phenyl carbonic ester with the concentration of 12mg/ml.
In 1000cd/m2Under luminous efficiency be 65.32cd/A.The efficiency of this OLED device is very good, in 1000cd/ m2Under voltage be 7.35V.
Embodiment 2
Use methyl benzol carbonate as the solvent of luminescent layer, prepare have the layer through printing through ink jet printing OLED device.The structure of pixelation OLED device is glass/ITO/HIL (40nm)/HTM (20nm)/EML (60nm)/HBL (10nm)/ETL (40nm)/Al, thus in substrate prefabricated embankment to form pixelation device.In this case, green hair Luminescent material is dissolved in methyl benzol carbonate with the concentration of 19mg/ml.
In 1000cd/m2Under luminous efficiency be 42.27cd/A.The efficiency of this OLED device is very good, in 1000cd/ m2Under voltage be 10.56V.
The measured value of all embodiments is summarised in the following table 4.
Table 4: the measured value of Examples 1 and 2

Claims (23)

1. a kind of preparation, containing at least one organic functional material and at least the first organic solvent, wherein described first is organic Solvent contains at least one carbonate group, preferably a carbonate group.
2. preparation according to claim 1, wherein first organic solvent containing a carbonate group is basis The solvent of the carbonate-containing group of logical formula (I)
Wherein
R1And R2It is identical or different at each occurrence, and be the alkyl or alkoxy base of the straight chain with 1 to 20 carbon atom Group or branch or cricoid alkyl or alkoxy base with 3 to 20 carbon atoms, the straight chain with 2 to 20 carbon atoms Alkenyl or alkenyloxy group group or branch or cricoid alkenyl or alkenyloxy group group with 3 to 20 carbon atoms, or have 2 to 20 The alkynyl or alkynyloxy moieties of the straight chain of a carbon atom or branch or cricoid alkynyl or alkynyloxy group with 3 to 20 carbon atoms Group, wherein one or more non-adjacent CH2Group can be by-O- ,-S- ,-NR3-、-CONR3,-CO-O- ,-C=O- ,-CH =CH- or-C ≡ C- is replaced, and wherein one or more hydrogen atoms can be replaced by F, or the aryl with 4 to 14 carbon atoms Or heteroaryl groups, or condensed heterocycle or aryl can be formed and can be by one or more non-aromatic R3Group replaces, And multiple substituent Rs on same ring or on two different rings3It can be formed together monocycle or polycyclic aliphatic series or virtue again Race's ring system, the ring system can be by multiple substituent Rs3Replace；And
R3It is identical or different in each case, and be the alkyl or alkoxy base of the straight chain with 1 to 20 carbon atom, Or branch or cricoid alkyl or alkoxy base with 3 to 20 carbon atoms, wherein one or more non-adjacent CH2Base Group can be replaced by-O- ,-S- ,-CO-O- ,-C=O- ,-CH=CH- or-C ≡ C-, and wherein one or more hydrogen atoms can quilt F is replaced, or has 4 to 14 carbon atoms and can be by one or more non-aromatic R3The aryl or heteroaryl base that group replaces Group.
3. preparation according to claim 2, wherein first organic solvent containing a carbonate group is basis The solvent of the carbonate-containing group of logical formula (I)
Wherein
R1And R2It is identical or different at each occurrence, and be the aryl or heteroaryl group with 4 to 14 carbon atoms, or Person can form condensed heterocycle or aryl and can be by one or more non-aromatic R3Group replace, and on same ring or Multiple substituent Rs on two different rings3It can be formed together monocycle or polycyclic aliphatic series or aromatics ring system again, the ring system can By multiple substituent Rs3Replace.
4. preparation according to claim 2, wherein first organic solvent containing a carbonate group is basis The solvent of the carbonate-containing group of logical formula (I)
Wherein
R1It is the alkyl or alkoxy base or branch or ring with 3 to 20 carbon atoms of the straight chain with 1 to 20 carbon atom The alkyl or alkoxy base of shape, the alkenyl or alkenyloxy group group of the straight chain with 2 to 20 carbon atoms or have 3 to 20 carbon The branch of atom or cricoid alkenyl or alkenyloxy group group, or the alkynyl or alkynyloxy group base of the straight chain with 2 to 20 carbon atoms Group or branch or cricoid alkynyl or alkynyloxy moieties with 3 to 20 carbon atoms, wherein one or more non-adjacent CH2 Group can be by-O- ,-S- ,-NR3-、-CONR3,-CO-O- ,-C=O- ,-CH=CH- or-C ≡ C- replace, and one of them Or multiple hydrogen atoms can be replaced by F；And
R2It is the aryl or heteroaryl group with 4 to 14 carbon atoms, or condensed heterocycle or aryl can be formed and can By one or more non-aromatic R3Group replaces, and multiple substituent Rs on same ring or on two different rings3Again may be used It is formed together monocycle or polycyclic aliphatic series or aromatics ring system, the ring system can be by multiple substituent Rs3Replace.
5. preparation according to claim 2, wherein first organic solvent containing a carbonate group is basis The solvent of the carbonate-containing group of logical formula (I)
Wherein
R1And R2It is identical or different at each occurrence, and be the alkyl or alkoxy base of the straight chain with 1 to 20 carbon atom Group or branch or cricoid alkyl or alkoxy base with 3 to 20 carbon atoms, the straight chain with 2 to 20 carbon atoms Alkenyl or alkenyloxy group group or branch or cricoid alkenyl or alkenyloxy group group with 3 to 20 carbon atoms, or have 2 to 20 The alkynyl or alkynyloxy moieties of the straight chain of a carbon atom or branch or cricoid alkynyl or alkynyloxy group with 3 to 20 carbon atoms Group, wherein one or more non-adjacent CH2Group can be by-O- ,-S- ,-NR3-、-CONR3,-CO-O- ,-C=O- ,-CH =CH- or-C ≡ C- is replaced, and wherein one or more hydrogen atoms can be replaced by F.
6. preparation according to claim 2, wherein first organic solvent containing a carbonate group is basis The solvent of the carbonate-containing group of logical formula (I)
Wherein
R1It is the alkyl of the straight chain with 1 to 20 carbon atom or the alkane of alkoxy base or the branch with 3 to 20 carbon atoms Base or alkoxy base, the alkenyl or alkenyloxy group group of the straight chain with 2 to 20 carbon atoms or with 3 to 20 carbon atoms The alkenyl or alkenyloxy group group of branch, or the straight chain with 2 to 20 carbon atoms alkynyl or alkynyloxy moieties or have 3 to 20 The alkynyl or alkynyloxy moieties of the branch of a carbon atom, wherein one or more non-adjacent CH2Group can by-O- ,-S- ,- NR3-、-CONR3,-CO-O- ,-C=O- ,-CH=CH- or-C ≡ C- replace, and wherein one or more hydrogen atoms can be by F Instead of；And
R2It is cricoid alkyl or alkoxy base with 3 to 20 carbon atoms, the cricoid alkene with 3 to 20 carbon atoms Base or alkenyloxy group group, or cricoid alkynyl or alkynyloxy moieties with 3 to 20 carbon atoms, wherein one or more non-phases Adjacent CH2Group can be by-O- ,-S- ,-NR3-、-CONR3,-CO-O- ,-C=O- ,-CH=CH- or-C ≡ C- replace, and its Middle one or more hydrogen atom can be replaced by F.
7. according to claim 1 to one or more preparations in 6, wherein the surface tension of first solvent >= 25mN/m。
8. according to claim 1 to one or more preparations in 7, wherein in terms of the solvent total amount in the preparation, The content of first solvent is within the scope of 50 to 100 volume %.
9. according to claim 1 to one or more preparations in 8, wherein the boiling point of first solvent 100 to Within the scope of 400 DEG C.
10. according to claim 1 to one or more preparations in 9, wherein the preparation includes at least one different In the second solvent of first solvent.
11. according to claim 1 to one or more preparations in 10, wherein the boiling point of second solvent is 100 To within the scope of 400 DEG C.
12. according to claim 1 to one or more preparations in 11, wherein at least one organic functional material Solubility in first solvent and in second solvent is within the scope of 1 to 250g/l.
13. according to claim 1 to one or more preparations in 12, wherein the surface tension of the preparation 1 to Within the scope of 70mN/m.
14. according to claim 1 to one or more preparations in 13, wherein the viscosity of the preparation 1 to 50mPa.Within the scope of s.
15. according to claim 1 to one or more preparations in 14, wherein with the total weight of the preparation, institute The content of at least one organic functional material in preparation is stated within the scope of 0.001 to 20 weight %.
16. according to claim 1 to one or more preparations in 15, wherein at least one organic functional material Selected from organic conductor, organic semiconductor, organic fluorescent compounds, Phosphorescent compound, organic light-absorbing compound, You Jiguang Quick compound, organic photosensitizer and other organic photoactive compounds such as transition metal, rare earth element, lanthanide series and actinium series member The metal-organic complex of element.
17. preparation according to claim 16, wherein at least one organic functional material is selected from fluorescent illuminant, phosphorus Light illuminator, material of main part, host material, exciton-blocking material, electron transport material, electron injection material, hole conductor material Material, hole-injecting material, n-type dopant, p-type dopant, wide bandgap material, electron-blocking materials and hole barrier materials.
18. preparation according to claim 16, wherein at least one organic functional material is to inject material selected from hole Material, hole mobile material, luminescent material, electron transport material and electron injection material organic semiconductor.
19. preparation according to claim 18, wherein at least one organic semiconductor is selected from hole injection and hole Transmission material.
20. preparation according to claim 19, wherein hole injection and hole mobile material be polymerizable compound or The blend of person's polymerizable compound and non-polymeric compound.
21. a kind of prepare according to claim 1 to the method for one or more preparations in 20, wherein by described at least A kind of organic functional material is mixed at least first solvent.
22. a kind of method for preparing electroluminescent device, wherein at least one layer of the electroluminescent device is in the following manner Preparation will be deposited, be preferably printed on surface and then be done to one or more preparations in 20 according to claim 1 It is dry.
23. a kind of electroluminescent device, wherein at least one layer is prepared in the following manner, will be according to claim 1 in 20 One or more preparation depositions are preferably printed on surface and are subsequently dried.
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